bluuebunny/crossref_metadata_2025 huggingface dataset:
The Brazilian Tenentes after the Revolution of 1930
Authors: Alexander Robert J.
Published: March 2007

The “Tenentes” or “lieutenants” were an important factor in Brazilian politics between 1922 and the end of the government of President Castelo Branco early in 1967. They had an active and occasionally decisive role in most major political events for almost half a century. The emergence of the Tenentes in the 1920s was part of a broader movement of discontent with the Old Republic, a relatively loose confederation of states dominated by rural landed interests and the politicians associated with them. Subsequently, the Tenentes played a key part in overthrowing the Old Republic in the Revolution of 1930.

Getúlio Vargas came to power in the 1930 Revolution and stayed in the presidency for fifteen years. As provisional chief executive for more than three years, he suppressed a serious revolt against his authority by the state of Sao Paulo between July and October of 1932, and summoned the assembly that wrote the Constitution of 1934 and chose him to be the first president under it.
Trade Intensification in the Central American Common Market
Authors: Christou G. , Wilford W. T.
Published: March 2007

The movement toward regional integration is one of the more important features of international economic relations between developing nations during the past decade, and none has been more ambitious in the developing world than the attempt of the five countries of Central America to band together in the Central American Common Market (CACM). The CACM was a dominant force in Central American economic development throughout the decade of the 1960s, and sufficient data are now available to make preliminary judgments about the effects of economic integration upon the intra- and extraregional trade patterns of the isthmus.

The model used in the ensuing analysis is similar to the one postulated by Savage and Deutsch (1960) and Goodman (1963: 197), and is a useful step in preliminary analysis of flow data such as trade flows among countries. The model does not seek to explain such flows, but rather to adjust them or remove the effect of the trade-size factor.
The Andean Common Market: A New Thrust at Economic Integration in Latin America
Authors: Kearns Kevin C.
Published: March 2007

The decade of the 1960s could well be termed the First Economic Integration Decade in Latin America. During this period the republics of Latin America experienced a “collective awakening,” inspiring an environment in which superficial and exclusivist values gave way to pragmatic and cooperative attitudes. Economic alliances were formed among neighbors, predicated on the rationale that, by joining forces in the spirit of cooperation and applying an ecumenical approach to common problems, each of the participating countries would be better off than pursuing a strictly autarkic course (see Figure 1).

The initial effort at integration was the Central American Common Market (CACM), formed in late 1960 and including all the countries of Central America except Panama.1 That same year, the Latin American Free Trade Association (LAFTA) was created and, measured in terms of territory and population, represented the most significant economic cooperative. A third grouping was the Caribbean Free Trade Association (CARIFTA), established in 1968 as an agreement among eleven British Commonwealth nations and territories.
U.S. Influence in the Organization of American States
Authors: Meek George
Published: March 2007

Literature on U.S. influence in the Organization of American States reveals a marked diversity of views. Some authors consider that U.S. influence is absolute or very nearly so; others hold that it is relative; still others think it is minimal.

In the nearly-absolute school, former Guatemalan President Arévalo (1961: 126) says that the United States “always wins” in the OAS. The Ecuadorian writer Benjamín Cardón (1965: 29) says that the OAS “receives orders and complies with them, with the appearance of discussion, and the appearance of votes that satisfy pro-forma the hypocritical quakerism of the masters.” This view might be summed up by a comment attributed to a Latin American delegate to one Inter-American Conference: “If the United States wanted to badly enough, it could have a resolution passed declaring two and two are five ” (New York Times, March 8, 1954).
Canada's First Diplomatic Missions in Latin America
Authors: Murray D. R.
Published: March 2007

Canada became the odd man out in the Western Hemisphere when it declared war on Germany on September 10, 1939. Other than the Caribbean colonies of the various European belligerents, Canada was the only American country to become an active participant in the European war. The decision to go to war had been freely made by Parliament, but it was clearly determined by Canada's historic ties as a member of the British Commonwealth. As the only independent belligerent in the Americas, Canada's position clearly was anomalous, and the makers of Canadian foreign policy had to go to considerable effort trying to overcome the problems Canada faced as a nation at war in a hemisphere trying to avoid war.
Organizational Bureaucracy in Latin America and the Legacy of Spanish Colonialism
Authors: Hanson Mark
Published: March 2007

As Latin American nations begin to marshal their rapidly growing human and material resources, they frequently encounter organizational infrastructures which are incapable of supporting the rapid process of modernization. Yet, these inadequate infrastructures seem to persist over time, leaving behind unrecoverable losses. Attempts to understand the problems of modernization must not only consider questions of social and economic development, but also questions reflecting on the development of organizational and administrative processes.

The central theme of this paper is the argument that the organizational and administrative mechanisms of societal and institutional governance have never quite broken loose from the historic legacy of Spanish colonialism and that the needs of modernizing nations are basically being served by administrative dinosaurs. Other writers have addressed themselves to the theme regarding the influence of colonial institutions on modern life, but the tendency has been to select general administrative practices and trace them across many nations in various periods of time.
A Profile of Amazonia: Its Possibilities for Development
Authors: Foland Frances M.
Published: March 2007

Amazonia is once again the nouvelle vague. Object of intense but ephemeral attention at the turn of the century and intermittently thereafter, the region now confronts a concerted and multipronged program for its de facto integration into the nation.

A special issue of Desenvolvimento & Conjuntura in March 1967, devoted to Amazonia, editorialized: “O atual interêsse pela Amazônia resulta de duas cadeias causais, de grande profundidade, e que são; primeiro, a consciência nacional da necessidade de acelerar o desenvolvimento de todo o territorio nacional, visando à terminação dos desniveis econômicos; e, segundo a compreensão que temos atualmente de fatôres de âmbito internacional. Estamos cônscios de que chegamos a era do desenvolvimento regional.”
Military Institutional Development and Sociopolitical Change: The Bolivian Case
Authors: Corbett Charles D.
Published: March 2007

The Latin American military is a complex institution in a complex society. It probably has always been, but in the past the dynamics acting upon the change versus order equation have allowed new structural relationships to be worked out over extended periods of time, relatively free from ideological passions and exogenous influences. That time has passed. Probably in no other region of the world are military establishments undergoing the degree of institutional selfexamination and mission redefinition as are the armies of Latin America today. They have neither the development-oriented self-confidence of the armies of the “new” nations, nor the threat-orientedWeltanschauungof the military in the established countries. Previously acceptable roles—as moderators in the political process or guarantors of their own image of the country's traditions—are under examination not only in the society at large but in the heart of the military institutions.
Voluntary Associations in Rio, 1870-1945: A New Approach to Urban Social Dynamics
Authors: Conniff Michael L.
Published: March 2007

During the late Empire in Brazil, Rio de Janeiro society felt the stirrings of a new process, one which would seriously alter—and threaten—the traditional way of life in the city. In imitation of Europe, well-to-do citizens began forming voluntary associations for mutual aid and protection. The trend soon reached the middle and upper levels of the proletariat, whose organizations became labor unions. Most sectors of the urban society gradually organized around interest groups, and as the city surged into the new century with over a half-million people, occasional conflict marred the society of “conciliation and reform.” By the 1920s, with the sobering experiences of Europe, Russia, and Mexico in mind, thoughtful Brazilians called for conservative social policy to contain class conflict. Many blamed the excessive liberalism of republican government since 1889 and harked back to medieval institutions for bringing social peace.
Power Structure and Patronage in a Community of the Dominican Republic
Authors: Walker Malcolm T.
Published: March 2007

In this paper it is intended to present the “political ethnography” of Villalta, a community in the Dominican Republic, from the period before the rise of Trujillo until May 1968, when municipal elections were held throughout the country. The principal concern is to show how the power structure and system of patronage which developed in Villalta during the Trujillo years has responded to the political fortunes of the country since the death of Trujillo.

Much of the discussion will deal with a small group of men who are the principal dispensers of political patronage and who, over the years, have represented the community to the outside. At lower levels, those who acquiesce to the judgment of these men frequently do so in accordance with patron-client ties. Because of both political and economic change within and outside the community, the basis on which this acquiescence has rested, has undergone change and the position of the power-holders has been rendered more tenuous.
U.S. Control Over Cuban Sugar Production, 1898-1902
Authors: Hitchman James H.
Published: March 2007

For years many Americans have assumed that the United States has exploited Cuba. The greatest opportunity for this control existed when the United States occupied Cuba after the Spanish-American War. The island was ravaged by war, famine, and disease, and the Cubans were exhausted after nearly a decade of depression, and revolution. It would have been easy for the U.S. government and business interests to control Cuba economically. Yet this did not occur. By concentrating our attention upon Cuban sugar production, perhaps the real nature of United States-Cuban economic relations may become apparent.

In the aftermath of the Spanish-American War, the McKinley administration found itself caught between two forces. The Congressional Joint Resolution of April 20, 1898, bound the Americans to leave Cuba once the island was pacified, but the Paris Peace Treaty of December 10, 1898, assumed that the United States would remain for a period of reconstruction.
Social Security Policy and the Working Class in Twentieth-Century Brazil
Authors: Malloy James M.
Published: March 2007

A crucial feature of political life in twentieth-century Brazil has been the growing role of the state as the central regulator of social, economic, and political life. One aspect of the expansion of the public sector in Brazil, as elsewhere, has been the accumulation by the state of a number of important social and economic functions previously exercised outside the public domain. One important function adopted by the state in Brazil is that of social protection, in the form of an elaborate and complex social insurance system. Presently some form of social protection reaches almost the entire rural population and some 78 percent of the urban population. The main social protection organization—Instituto Nacional da Previdência Social (INPS)— boasts the second largest budget in the nation (in 1975 CR $43 billion in contrast to the federal budget of Cr $113 billion) and a bureaucracy of over 102,700 employees.
A Review of Development Planning in Guatemala
Authors: Hoy Don R.
Published: March 2007

Planning is often analogous to weather in that everyone discusses it but little is really done. Such, at least, is the case in Guatemala where individuals, groups, and the government espouse a need for development planning in eloquent terms but produce few positive results. In Guatemala, however, it is increasingly recognized that planning can be a logical and relatively scientific method of improving resource utilization. The purpose of this paper is to appraise a few general aspects of development planning in Guatemala and to characterize its organizational structure and the political constraints imposed upon the process.

Governments are assuming a more dominant role in development, particularly in the less advanced areas. Public opinion has generally supported this trend by criticizing development programs or blaming the lack of development on the government.
Hull and Argentina: Wilsonian Diplomacy in the Age of Roosevelt
Authors: Woods Randall B.
Published: March 2007

In 1943 a small group of ultra-nationalist Argentine army officers, including the youthful and ambitious Juan Domingo Perón, utilized its control of key Cabinet posts to achieve absolute dominance within the government of General Pedro Ramírez. Blatantly invoking fascist Germany as a model for national emulation, this clique launched an expansionist program aimed at creating an Argentine-dominated neutralist bloc in southern South America. The State Department, under the direction of Secretary Cordell Hull, responded to Argentine aggression by providing military aid to Argentina's neighbors, laying plans to impose stiff economic sanctions and threatening to publish intelligence data linking certain Argentine officials with Axis espionage and sabotage rings operating in South America. U.S. pressure produced immediate results: Ramírez broke with the pro-Axis, expansionist group within his administration and severed diplomatic relations with Germany, Italy, and their allies.
Colombian Political Bases of the Andean Pact Statute on Foreign Capitals: National Influences on International Regulation of Foreign Investment
Authors: Sherman Gail Richardson
Published: March 2007

Recognition of the economic power of multinational corporations has stimulated speculation about the development of international political structures to regulate this power. A major difficulty in assuming that corporate expansion throughout the world will give rise to political phenomena of similar scope lies in the difference between international power based on corporate growth and international power based on the cooperation of nation-states. Whereas the economic internationalism of corporations is in general an expansion of power which has well-defined historical foundations in ideology and organization, the task of developing international political associations with power to enforce policy within a number of states entails at least a partial redefinition of traditional bases of political sovereignty. The former is growth of existing power; the latter is creation of a new form of power. There is no obviously necessary development from one to the other.
Jobs and Housing: Alternative Developments in the Venezuelan Guayana
Authors: MacDonald John Stuart , MacDonald Leatrice D.
Published: March 2007

The appraisal of development projects is often complicated by the fact that they rarely occur in isolation. In Latin America, the effectiveness of public housing programs and the reactions of the people involved are, as a rule, bound up with the whole complex of heterogeneous developments we call “urbanization.” And when public housing reaches the villages, it typically goes hand in hand with agrarian reform. This is generally the case in Venezuela, where large public housing schemes have been in operation since 1958.

Consequently it is difficult to disentangle and then evaluate the impact of industrialization per se from social infrastructure development in the towns, or agrarian reform per se from social infrastructure development in the villages. The Guayana region of Venezuela is one of the few areas where a production-oriented project and a social welfare project have operated discretely, but within a uniform socioeconomic context.
Impressions of the Peruvian Agrarian Reform
Authors: Gitlitz John Stephen
Published: March 2007

On 24 June 1969 the military government of Peru, exercising its de facto power to issue legislation by decree, promulgated a law of agrarian reform. In Latin America legal norms—even radical ones—are not necessarily to be feared. Many countries have agrarian reform laws and in most of these agrarian structures have not been changing rapidly. Indeed, the previous administration in Peru had passed a mild law in 1964, but the hacienda structure of the Peruvian Andes remained virtually intact. Few feared that the new code enacted by the military would present a strong challenge to tradition.

Forty-eight hours after its promulgation opinions began to change. The government announced that interventors were being sent to eight of the largest sugar estates on the northern coast. Intervention is the first step toward expropriation. The sugar estates lie at the heart of the Peruvian oligarchy: they were exempt from the 1964 legislation.
The Politics of Labor Protest in Mexico
Authors: Handelman Howard
Published: March 2007

In years past, Mexico's political system was often cited as a model for political development in the “third world” (Scott, 1974, 1965). While most Latin American governments allowed associational interest groups little opportunity to articulate their needs and demands, Mexico's ruling party (the PRI) provided institutionalized representation for three major segments of the nation's population: the agrarian sector (peasants and agricultural workers); the middle class (the “popular sector”); and organized labor unions. Anderson and Cockcroft (1966: 16) indicated that “the Mexican national leadership seem … to be committed to tolerating a substantial amount of political pluralism. It is taken for granted … that occupational groups attempt to promote their interests and demands through organizations.”

More recently, however, a “revisionist” group of political scientists has disputed the contention that Mexico is moving toward democratic pluralism; instead they characterize its political system as essentially authoritarian (Purcell, 1973; Johnson, 1971; Stevens, 1970; Davis and Coleman, 1974). In this article I shall examine the degree of latitude which the Mexican political system allows independent labor movements I in articulating the demands of their members and in pressing I those demands on the ruling party.
The Role of the Law Graduate in the Political Elite of Imperial Brazil
Authors: Barman Roderick , Barman Jean
Published: March 2007

By the application of fresh analytical approaches such as prosopography and the concepts of “secular trend” and “conjuncture” pioneered by the Annales school, historians are at last beginning to probe the social and political structures of Latin America in the national period. What before had been surmised or supposed, particularly in regard to the dominance of political and social life by elites, can now be quantitatively confirmed, while the identification of secular trends permits the historian to penetrate behind the confusion of the incidentals to the basic characteristics of the different nations and their evolution over time.

The standard interpretation of Imperial Brazil (1822-1889) has until recently been that of a stable but anomalous monarchy dominated for most of its existence by its ruler Pedro II. The aging of the Emperor, the abolition of slavery on which the regime is conceived as being based, the discontents of the military, and the inevitable advance of Republicanism have been taken as the principal causes for the collapse of the Brazilian Empire on November 15, 1889.
U.S.-Panamanian Relations since 1941
Authors: Langley Lester D.
Published: March 2007

Since 1941 United States relations with Latin American countries have fluctuated between the ofñcial cordiality of wartime cooperation, which provided the basis for the Organization of American States and the Rio Treaty, and deep-seated hostility and malaise, which erupted in the Nixon visit and in Castro's revolution, as well as in more recent unpleasant incidents. Latin American leaders have contended that the United States violated its wartime commitments, particularly in the economic sphere, by concentrating on the recovery of Europe in the first postwar decade and on Asian upheaval in the second. The history of U.S.-Panamanian relations since 1941 provides an excellent case study in order to test the validity of these contentions.
Industrialists and Politics in Argentina: An Opinion Survey of Trade Association Leaders
Authors: Freels John W.
Published: March 2007

The role of the Latin American industrialist as a potential modernizing agent promoting social and economic evolution has received increasing attention in recent years. Yet discussions of the industrialist's role have been largely impressionistic; few opinion surveys of the industrialist's goals and values are available. This study was based on such an opinion survey of industrial trade association leaders in Argentina, a nation in which the debate over the role of the industrialist in social evolution has received wide attention.

The industrial trade association movement itself is split into two factions: the porteño-dominaied Argentine Industrial Union (UIA), created before the turn of the century, and the interior-based Confederation of Industry (CI), founded during the second presidency of Juan Domingo Perón. The ability of the sector to strengthen its political position hinges largely on the need to develop greater rapport between these two groups of industrialists.
Patterns of Lumbar Region Movement During Trunk Lateral Bending in 2 Subgroups of People With Low Back Pain
Authors: Gombatto Sara P , Collins David R , Sahrmann Shirley A , Engsberg Jack R , Van Dillen Linda R
Published: March 2007

Background and Purpose

The movement system impairment (MSI) system is one proposed system for classifying low back pain (LBP) problems. Prior clinical data and observations for the MSI system suggest that different LBP subgroups demonstrate different patterns of movement during clinical tests, such as trunk lateral bending (TLB). The purpose of this study, therefore, was to examine the validity of the observation that lumbar region (LR) movement patterns during TLB are different between 2 subgroups of people with LBP: lumbar rotation with extension (Rotation With Extension) and lumbar rotation (Rotation).

Subjects

Participants were 44 people (28 men and 16 women; age [X̄±SD], 28.5±8.4 years) with chronic or recurrent LBP.

Methods

Each participant's LBP problem was classified with the MSI system. Kinematic variables were measured, and LBP symptoms were recorded during the TLB test.

Results

People in the 2 LBP subgroups demonstrated different patterns of LR movement during TLB. People in the Rotation With Extension subgroup displayed an asymmetric (right versus left) pattern of LR movement across the TLB movement, whereas people in the Rotation subgroup displayed a symmetric pattern of LR movement. Equal proportions of people in the 2 subgroups reported an increase in symptoms with the TLB test.

Discussion and Conclusion

The patterns of LR movement across the TLB movement were different in 2 subgroups of people with LBP. The difference in the LR movement patterns between subgroups may be an important factor to consider in specifying the details of the interventions for these 2 LBP problems.
Preliminary Examination of a Proposed Treatment-Based Classification System for Patients Receiving Physical Therapy Interventions for Neck Pain
Authors: Fritz Julie M , Brennan Gerard P
Published: March 2007

Background and Purpose

Neck pain frequently is managed by physical therapists. The development of classification methods for matching interventions to subgroups of patients may improve clinical outcomes. The purpose of this study was to describe a proposed classification system for patients with neck pain by examining data for consecutive patients receiving physical therapy interventions.

Subjects and Methods

Standardized methods for collecting baseline and intervention data were used for all patients receiving physical therapy interventions for neck pain over 1 year. Outcome variables were the Neck Disability Index (NDI), numeric pain rating, and number of visits. Treatment was provided at the discretion of the physical therapist. After the completion of treatment, each patient was classified by use of baseline variables. The interventions received by the patient were categorized as being matched or not matched to the classification. Outcomes for patients who received matched interventions were compared with those for patients who received nonmatched interventions. The interrater reliability of the classification algorithm was examined with a subset of 50 patients.

Results

A total of 274 patients were included in this study (74% women; age [X̄±SD]=44.4±16.0 years). The most common classification was centralization (34.7%); next were exercise and conditioning (32.8%) and mobility (17.5%). The interrater reliability for classification decisions was high (kappa=.95, 95% confidence interval [CI]=0.87–1.0). A total of 113 patients (41.2%) received interventions matched to the classification. Receiving matched interventions was associated with greater improvements in the NDI (mean difference=5.6 points, 95% CI=2.6–8.6) and in pain ratings (mean difference=0.74 point, 95% CI=0.21–1.3) than receiving nonmatched interventions.

Discussion and Conclusion

The development of classification methods for patients with neck pain may improve the outcomes of physical therapy intervention. This study was done to examine a previously proposed classification system for patients receiving physical therapy interventions for neck pain. Receiving interventions matched to the classification system was associated with better outcomes than receiving nonmatched interventions. Although the design of this study prohibited drawing conclusions about the effectiveness of the system, the results suggest that further research on the system may be warranted.
Correction of Clawed Hallux Deformity: Comparison of the Jones Procedure and FHL Transfer in a Cadaver Model
Authors: Elias Fady N. , Yuen Tracy J. , Olson Soren L. , Sangeorzan Bruce J. , Ledoux William R.
Published: March 2007

Background: A clawed hallux is defined as extension of the first metatarsophalangeal (MTP) joint combined with flexion of the interphalangeal (IP) joint. Two operative procedures, the modified Jones procedure and flexor hallucis longus (FHL) transfer, are indicated for correction. The purpose of this study were to evaluate the overall effectiveness of these two procedures in correcting both the clawed hallux deformity and its mechanical consequences and to compare their effect on postoperative plantar pressures. Methods: The modified Jones procedure and FHL transfer were done on cadaver specimens that were tested before and after surgery in a specialized foot-loading frame. We quantified the angular correction of the MTP and the IP joints, as well as the plantar pressures under the head of the first metatarsal and the hallux. Results: Both surgeries were equally effective in correcting the angular deformity at the MTP and IP joints ( p = 0.037 and 0.0020, respectively). A significant reduction in the plantar pressure ( p = 0.015) beneath the first metatarsal was observed with both the modified Jones procedure and the FHL transfer. Overall, there was no significant difference between preoperative and postoperative pressures beneath the hallux ( p = 0.5); however, for the FHL overpull group there was significantly less pressure beneath the hallux after surgery ( p = 0.014). Conclusions: The two surgeries produced similar results, but the FHL transfer does not require fusion of the hallux, which is considered an undesirable co-morbidity of the modified Jones procedure.
Chiral Ionic Phosphites and Diamidophosphites: A Novel Group of Efficient Ligands for Asymmetric Catalysis
Authors: Gavrilov Konstantin N. , Lyubimov Sergey E. , Bondarev Oleg G. , Maksimova Marina G. , Zheglov Sergey V. , Petrovskii Pavel V. , Davankov Vadim A. , Reetz Manfred T.
Published: March 2007

Seven members of a new class of chiral P‐monodentate cationic phosphites and diamidophosphites have been synthesized for the first time and tested as ligands in asymmetric transition metal catalysis. Up to 96 % ee was achieved in the rhodium‐catalyzed asymmetric hydrogenation of functionalized olefins and up to 99 % ee in the palladium‐catalyzed allylic allylation. Applications of the immobilized cationic rhodium complex to asymmetric catalytic synthesis have also been demonstrated.
Highly Efficient Asymmetric Hydrogenation of α,β‐Unsaturated Carboxylic Acids Catalyzed by Ruthenium(II)‐Dipyridylphosphine Complexes
Authors: Qiu Liqin , Li Yue‐Ming , Kwong Fuk Yee , Yu Wing‐Yiu , Fan Qing‐Hua , Chan Albert S. C.
Published: March 2007

Two types of catalysts [RuL(benzene)Cl]Cl and Ru(OCOCH3)2L with the dipyridylphosphine ligands P‐Phos and Xyl‐P‐Phos were applied in the asymmetric hydrogenation of α,β‐unsaturated carboxylic acids. The cationic complexes [RuL(benzene)Cl]Cl were found to be superior to the corresponding neutral complex Ru(OCOCH3)2L in this type of reactions. The catalysts exhibited excellent activities and enantioselectivities (up to 97 % ee) in the asymmetric hydrogenation.
Continuous, Ionic Liquid‐Catalysed Propylation of Toluene in a Liquid‐Liquid Biphasic Reaction Mode using a Loop Reactor Concept
Authors: Ladnak Viktor , Hofmann Norbert , Brausch Nicole , Wasserscheid Peter
Published: March 2007

Acidic ionic liquids of the type [cation] [bis(trifluoromethanesulfonyl)imide anion]/aluminium trichloride {[cation][(CF3SO2)2N]/AlCl3} have been applied to realise for the first time a continuous Friedel–Crafts alkylation reaction in liquid‐liquid biphasic reaction mode using a loop reactor concept. Exemplified for the continuous propylation of toluene we have proved that the acidic catalyst layer is successfully immobilised over at least 18 h in the loop reactor. After 8 h time‐on‐stream, a steady state has been reached followed by at least 10 h time‐on‐stream without any loss of activity or change in selectivity. Our results reveal the high potential of this class of acidic ionic liquids in continuous arene functionalisation reactions.
A Comparative Study of the Synthesis of 3‐Substituted Catechols using an Enzymatic and a Chemoenzymatic Method
Authors: Berberian V. , Allen C. C. R. , Sharma N. D. , Boyd D. R. , Hardacre C.
Published: March 2007

A series of cis‐dihydrodiol metabolites, available from the bacterial dioxygenase‐catalysed oxidation of monosubstituted benzene substrates using Pseudomonas putida UV4 , have been converted to the corresponding catechols using both a heterogeneous catalyst (Pd/C) and a naphthalene cis‐diol dehydrogenase enzyme present in whole cells of the recombinant strain Escherichia coli DH5α(pUC129: nar B). A comparative study of the merits of both routes to 3‐substituted catechols has been carried out and the two methods have been found to be complementary. A similarity in mechanism for catechol formation under both enzymatic and chemoenzymatic conditions, involving regioselective oxidation of the hydroxyl group at C‐1, has been found using deuterium labelled toluene cis‐dihydrodiols. The potential, of combining a biocatalytic step (dioxygenase‐catalysed cis‐dihydroxylation) with a chemocatalytic step (Pd/C‐catalysed dehydrogenation), into a one‐pot route to catechols, from the parent substituted benzene substrates, has been realised.
Simple Ruthenium Precatalyst for the Synthesis of Stilbene Derivatives and Ring‐Closing Metathesis in the Presence of Styrene Initiators
Authors: Lo Cheikh , Cariou Renan , Fischmeister Cédric , Dixneuf Pierre H.
Published: March 2007

The ruthenium complex RuCl2(p‐cymene)(IMes) was found to be an efficient precatalyst, with styrene as an initiating species, for the alkene metathesis of various styrenes into symmetrical and unsymmetrical stilbene derivatives and for the ring‐closing metathesis reaction of a sterically hindered olefin leading to a tetrasubstituted cycloolefin.
Synthesis of Enantiopure (S,R,S)‐ and (R,S,R)‐1,4,5,8,9,16‐Hexahydroxytetraphenylenes
Authors: Wu An‐Hui , Hau Chun‐Kit , Wong Henry N. C.
Published: March 2007

1,4,5,8,9,16‐Hexahydroxytetraphenylene (5) was synthesized by an iodobenzene diacetate‐mediated phenolic oxidation. Enantiopure forms of 1,4,5,8,9,16‐hexahydroxytetraphenylenes [(S,R,S)‐5 and (R,S,R)] were successfully synthesized either by using (S,S)‐and (R,R)‐1,8,9,16‐tetramethoxytetraphenylenes [(S,S)‐7 and (R,R)‐7] as starting materials or by direct resolution of 1,4,5,8,9,16‐hexahydroxytetraphenylene (5).
Tin‐Free Radical Carbonylation: Synthesis of Acylated Oxime Ethers Using Alkyl Allyl Sulfone Precursors, Carbon Monoxide, and Phenylsulfonyl Oxime Ether
Authors: Kim Sangmo , Lim Kyoung‐Chan , Kim Sunggak , Ryu Ilhyong
Published: March 2007

Acylated oxime ethers have been prepared by a three‐component coupling reaction using alkyl allyl sulfone precursors, carbon monoxide, and phenylsulfonyl oxime ether derivatives under tin‐free radical reaction conditions.
Diversity‐Oriented Preparation of Enantiopure Spirocyclic 2‐Azetidinones from α‐Oxo‐β‐lactams through Barbier‐Type Reactions followed by Metal‐Catalyzed Cyclizations
Authors: Alcaide Benito , Almendros Pedro , del Campo Teresa Martínez , Rodríguez‐Acebes Raquel
Published: March 2007

Novel, simple, and convenient strategies to diversely functionalized spirocyclic β‐lactams have been developed by using different metal‐mediated carbonyl addition/cyclization reaction sequences. Spirocyclization precursors, 2‐azetidinone‐tethered homoallylic alcohols, bromohomoallylic alcohols, homopropargylic alcohols, (buta‐1,3‐dien‐2‐yl)methanols, and α‐allenols have been obtained by regioselective addition of stabilized organometallic reagents to azetidine‐2,3‐diones in an aqueous environment. Ruthenium‐, silver‐, and palladium‐catalyzed reactions of the above monocyclic unsaturated alcohol derivatives provided oxaspiro‐β‐lactams.
Suppression of β‐Hydride Elimination in the Intramolecular Hydrocarboxylation of Alkynes leading to the Formation of Lactones
Authors: Huo Zhibao , Patil Nitin T. , Jin Tienan , Pahadi Nirmal K. , Yamamoto Yoshinori
Published: March 2007

Palladium‐catalyzed intramolecular cyclization of the alkynoic acids was studied which gave the five‐ and six‐membered lactones in moderate yields. The reaction can be conducted simply by heating a toluene solution of alkynoic acids at 100 °C in the presence of catalytic amounts of Pd(PPh3)4 and (o‐tol)3P. The key for this transformation is the use of phosphines, instead of carboxylic acids, as an additive. Similar to our previously developed catalytic system the use of carboxylic acid, instead of (o‐tol)3P, resulted into the exclusive formation of the diene.
Generation and Application of o‐Quinone Methides Bearing Various Substituents on the Benzene Ring
Authors: Sugimoto Hiromichi , Nakamura Satoshi , Ohwada Tomohiko
Published: March 2007

o‐Quinone methides (o‐QMs) are highly reactive, short‐lived intermediates, which have potential synthetic applicability. However, few studies on the generation of o‐QMs bearing an electron‐withdrawing group have been reported. Herein we present a general method for the generation of o‐QMs, particularly those substituted with an electrophilic substituent, from new precursors, 4H‐1,2‐benzoxazines 2. We have also studied systematically the Diels–Alder reactions of o‐QMs with various dienophiles, such as vinyl ethers, enamines and imines. The reactions provide a versatile route to substituted chromans, phenols and 3,4‐dihydro‐2H‐benzo[e][1,3]oxazines (3,4‐dihydro‐1,3‐benzoxazines). Furthermore, we applied the new method to the derivatization of some natural products.
Dehydrative Cyclization Catalyzed by the Combination of Molybdenum(VI) Oxides and Benzoic Acids: First Synthesis of the Antitumour Substance BE‐70016
Authors: Sakakura Akira , Umemura Shuhei , Kondo Rei , Ishihara Kazuaki
Published: March 2007

The dehydrative cyclization of N‐(o‐hydroxybenzoyl)threonine derivative 1a is efficiently promoted by the combined use of molybdenum(VI) oxides and benzoic acids bearing electron‐withdrawing substituents. In the presence of ammonium molybdate [(NH4)2MoO4, 10 mol %] and pentafluorobenzoic acid (C6F5CO2H; 10 mol %), dehydrative cyclization of 1a was conducted in toluene under azeotropic reflux conditions to give 2‐(o‐hydroxyphenyl)oxazoline 2a in 76 % yield. Furthermore, the first total synthesis of the antitumour substance BE‐70016 was achieved using the catalytic dehydrative cyclization of 1a as a key reaction.
Theoretical Studies on ortho‐Oxidation of Phenols with Dioxygen Mediated by Dicopper Complex: Hints for a Catalyst with the Phenolase Activity of Tyrosinase
Authors: Naka Hiroshi , Kondo Yoshinori , Usui Shinya , Hashimoto Yuichi , Uchiyama Masanobu
Published: March 2007

Theoretical studies on the chemo‐ and regioselective ortho‐oxidation reaction of phenols mediated by a biomimetic (μ–η2:η2peroxo)dicopper(II) complex were performed using unrestricted hybrid density functional theory (UB3LYP) calculations, with the aim of providing a guide for the development of new bio‐inspired catalysts with the phenolase activity of tyrosinase. Energetic, structural, and electronic analyses suggested the involvement of a side‐on (μ–η2:η2)‐Cu2O2 complex as an active intermediate, and a single electron transfer (SET)‐induced electrophilic aromatic substitution mechanism is proposed for the rate‐determining CO bond forming process; this is consistent with experimental observations. Moreover, the inherent roles of, and requirement for, two copper ions in this reaction have been elucidated.
A New Preparation of Homochiral N‐Protected 5‐Hydroxy‐3‐ piperidenes, Promising Chiral Building Blocks, by Palladium‐ Catalyzed Deracemization of Their Alkyl Carbonates
Authors: Takahata Hiroki , Suto Yumiko , Kato Erina , Yoshimura Yuichi , Ouchi Hidekazu
Published: March 2007

The palladium‐catalyzed deracemization of N‐protected alkyl carbonates of 5‐hydroxy‐3‐piperidenes by use of chiral phosphine ligands is described. A Trost ligand such as (R)‐BPA was found to be a suitable chiral ligand for the deracemization, providing N‐protected 5‐hydroxy‐3‐piperidenes in good yields with good to high enantioselectivities. A plausible mechanism for the reaction is proposed.
Peptidic Amidomonophosphane Ligand for Copper‐Catalyzed Asymmetric Conjugate Addition of Diorganozincs to Cycloalkenones
Authors: Soeta Takahiro , Selim Khalid , Kuriyama Masami , Tomioka Kiyoshi
Published: March 2007

Peptidic modification of (S)‐2‐[(diphenylphosphino)methyl]pyrrolidine gave a dipeptide‐connected amidomonophosphane ligand for the highly efficient, copper‐catalyzed asymmetric conjugate addition reaction of organozinc reagents with cycloalkenones, giving 3‐alkylated cycloalkanones in high enantioselectivity of up to 98 % ee. A model that predicts the stereochemistry of the reaction is discussed.
Polymer Incarcerated Ruthenium Catalyst for Oxidation of Alcohols with Molecular Oxygen
Authors: Matsumoto Tsutomu , Ueno Masaharu , Kobayashi Juta , Miyamura Hiroyuki , Mori Yuichiro , Kobayashi Shū
Published: March 2007

A polymer incarcerated ruthenium (PI Ru) catalyst for the oxidation of alcohols with molecular oxygen has been developed. The catalyst was prepared from a polystyrene‐based copolymer with ruthenium chloride hydrate as the metal source. The choice of ruthenium species was important to obtain high catalytic activity as well as for the suppression of leaching of ruthenium. In the presence of 5 mol % of PI Ru and 15 mol % of 2,2,6,6‐tetramethylpiperidine N‐oxyl (TEMPO), alcohols were oxidized using molecular oxygen at atmospheric pressure to afford the corresponding aldehydes or ketones in good to excellent yields. The catalyst could be recovered and reused at least ten times without loss of activity.
Catalytic Asymmetric Aldol Reactions of Enolizable Carbon Pronucleophiles with Formaldehyde and Ethyl Glyoxylate
Authors: Fukuchi Isao , Hamashima Yoshitaka , Sodeoka Mikiko
Published: March 2007

We herein describe novel catalytic asymmetric aldol reactions of acidic carbon pronucleophiles including β‐keto esters and specific ketones with reactive electrophiles such as formaldehyde and ethyl glyoxylate. In the presence of a catalytic amount of chiral Pd(II)‐BINAP complexes, the hydroxymethylation of β‐keto esters with paraformaldehyde or formalin was examined, and the corresponding adducts were obtained in good yields with good to high enantioselectivity (ca. 86 % ee). In some cases, the similar Pt(II) complex also worked well to give the products with better enantioselectivity. Furthermore, these complexes were found to promote the aldol reactions of less acidic ketones, and ethyl glyoxylate underwent reaction with 3‐coumaranone and β‐tetralone, affording the aldol products with a significant level of enantioselectivity of up to 83 % ee.
Asymmetric Total Synthesis of Nigerone and ent‐Nigerone: Enantioselective Oxidative Biaryl Coupling of Highly Hindered Naphthols
Authors: Kozlowski Marisa C. , Dugan Elizabeth C. , DiVirgilio Evan S. , Maksimenka Katja , Bringmann Gerhard
Published: March 2007

An enantioselective synthesis of the chiral bisnaphthopyrone natural product nigerone and its enantiomer, ent‐nigerone, has been realized. The use of constrained 2‐naphthol substrates was critical to producing highly functionalized chiral 1,1′‐binaphthols via asymmetric oxidative biaryl coupling with 1,5‐diaza‐cis‐decalin copper complexes. The final natural product was formed via a key eight‐step isomerization process of the coupling product, bisisonigerone, and proceeded with retention of the biaryl configuration. The axial configurations of bisisonigerone and nigerone were definitively established by a combination of circular dichroism (CD) measurements and quantum chemical CD calculations.
Reaction of Tetrahydropyranyl Ethers with Triethylsilyl Trifluoromethanesulfonate–2,4,6‐Collidine Combination: Speculation on the Intermediate, Efficient Deprotection, and Application to Efficient Ring‐Closing Metathesis as a Tether
Authors: Fujioka Hiromichi , Okitsu Takashi , Ohnaka Takuya , Sawama Yoshinari , Kubo Ozora , Okamoto Kazuhisa , Kita Yasuyuki
Published: March 2007

The reaction of tetrahydropyranyl (THP) ethers with triethylsilyl trifluoromethanesulfonate (TESOTf)–2,4,6‐collidine proceeded via collidinium salt intermediates to give the alcohol and 4‐triethylsiloxybutanal in good yields. The structure of the intermediate was confirmed by 1H NMR and FAB‐MS studies and by trapping it with EtOH. The reaction was applied for mild, efficient, and highly chemoselective deprotection method of THP ethers. The characteristic feature of the reaction is that the reaction conditions are weakly basic. Then, the reaction can proceed without affecting acid‐labile protecting groups. Furthermore, the intermediates from alkenol–THP ether were trapped with other alkenols to give acyclic mixed acetals, which were subjected to efficient ring‐closing metathesis by using the tetrahydropyranyl unit as a tether.
A Direct Organocatalytic Entry to Selectively Protected Aldopentoses and Derivatives
Authors: Grondal Christoph , Enders Dieter
Published: March 2007

The proline‐catalysed aldol reaction of 2,2‐dimethyl‐1,3‐dioxan‐5‐one with dimethoxyacetaldehyde is used as the key reaction according to the biomimetic C3+Cn strategy for de novo carbohydrate synthesis. Based on the Whitesides inversion strategy, protected D‐erythro‐pentos‐4‐ulose (de>96 %, ee=94 %) was employed for a rapid and divergent entry to various selectively and partly orthogonal protected aldopentoses and derivatives, like amino sugars, thio sugars, deoxy sugars, 4‐C‐substituted (alkylated) aldopentoses and epoxy sugars.
Effects of Aromatic Substituents on Binaphthyl‐Based Chiral Spiro‐Type Ammonium Salts in Asymmetric Phase‐Transfer Reactions
Authors: Kano Taichi , Lan Quan , Wang Xisheng , Maruoka Keiji
Published: March 2007

Spiro‐type phase‐transfer catalysts prepared from two equivalents of a single binaphthyl subunit were designed and applied to the asymmetric alkylation and direct aldol reactions of a glycine derivative. The effects of the substitution pattern of the binaphthyl subunits on the enantioselectivity were also investigated.
Catalytic Enantioselective Tandem Carbonyl Ylide Formation/1,3‐Dipolar Cycloaddition Reactions of α‐Diazo Ketones with Aromatic Aldehydes using Dirhodium(II) Tetrakis[N‐benzene‐fused‐phthaloyl‐(S)‐valinate]
Authors: Tsutsui Hideyuki , Shimada Naoyuki , Abe Takumi , Anada Masahiro , Nakajima Makoto , Nakamura Seiichi , Nambu Hisanori , Hashimoto Shunichi
Published: March 2007

The first successful example of the enantioselective intermolecular 1,3‐dipolar cycloaddition of a chiral dirhodium(II) catalyst‐associated carbonyl ylide with an aromatic aldehyde dipolarophile is described. The tandem carbonyl ylide formation/cycloaddition reactions of 1‐diazo‐5‐aryl‐2,5‐pentanediones with aromatic aldehydes using dirhodium(II) tetrakis[N‐benzene‐fused‐phthaloyl‐(S)‐valinate] as a catalyst provide exclusively exo cycloadducts in up to 92 % ee.
Enantioselective Reduction of 4‐Fluoroacetophenone at High Substrate Concentration using a Tailor‐Made Recombinant Whole‐Cell Catalyst
Authors: Gröger Harald , Rollmann Claudia , Chamouleau Francoise , Sebastien Isabelle , May Oliver , Wienand Wolfgang , Drauz Karlheinz
Published: March 2007

A practical and highly efficient biocatalytic synthesis of optically active (R)‐4‐fluorophenylethan‐1‐ol has been developed based on reduction of the corresponding 4‐fluoroacetophenone in the presence of a tailor‐made recombinant whole‐cell biocatalyst, containing an alcohol dehydrogenase and a glucose dehydrogenase. The reaction proceeds in a pure aqueous solvent media at a substrate concentration of ca. 0.5 M, and gives the desired product with high conversion (>95 %), good yield (87 %) and with an excellent enantioselectivity of >99 % ee. In addition, activity tests further showed that also the analogous 2‐ and 3‐fluoroacetophenones are promising substrates.
Dynamic Kinetic Resolution for the Catalytic Asymmetric Total Synthesis of Antithrombotic Agents M58163 and M58169
Authors: Saitoh Fumihiko , Nishida Hidemitsu , Mukaihira Takafumi , Aikawa Kohsuke , Mikami Koichi
Published: March 2007

Dynamic kinetic resolution is one of the most synthetically useful phenomena for asymmetric synthesis. Dynamic kinetic resolution for the catalytic asymmetric synthesis of a spiro[imidazo[1,2‐a]pyrazine‐2(3H),4′‐piperidin]‐5(1 H)‐one scaffold with a lanthanum‐linked BINOL complex is described. It is also clarified that starting materials, diamine 1 and keto ester 2, play important roles not only as substrates but also as additives to modify an active species of the lanthanum complex. The catalytic asymmetric total syntheses of our antithrombotic agents M58163 and M58169 have thus been achieved via dynamic kinetic resolution.
Asymmetric 1,4‐Addition of Organoboron Reagents to Quinone Monoketals Catalyzed by a Chiral Diene/Rhodium Complex: A New Synthetic Route to Enantioenriched 2‐Aryltetralones
Authors: Tokunaga Norihito , Hayashi Tamio
Published: March 2007

A novel synthetic approach to 2‐aryltetralones with high ee has been developed through asymmetric 1,4‐addition of arylboronic acids to naphthoquinone monoketals catalyzed by a rhodium complex with the (R,R)‐Ph‐bod* ligand. The asymmetric addition proceeded in high yields with excellent enantioselectivity.