bluuebunny/crossref_metadata_2025 huggingface dataset:
Natural Product Synthesis by C–H Functionalization: (–)-Zampanolide (Ghosh), Muraymycin D2 (Ichikawa), (+)-Sundiversifolide (Iwabuchi), (+)-Przewalskin B (Zhang/Tu), Artemisinin (Wu)
Authors: Taber Douglass F.
Published: November 2020

Arun K. Ghosh of Purdue University exposed (Org. Lett. 2011, 13, 4108) the ether 1 to DDQ. Hydride abstraction initiated nucleophilic addition of the allyl silane, which proceeded with high diastereocontrol to deliver 2, a key intermediate in the synthesis of (+)-zampanolide 3. Satoshi Ichikawa, after surveying (Org. Lett. 2011, 13, 4028) several N-protecting groups, settled on the phthalimide 4 as the best for directing the Du Bois oxidative cyclization. The sulfamate 5 was carried forward to a key component for the assembly of muraymycin D2 6. Yoshiharu Iwabuchi of Tohoku University found (Org. Lett. 2011, 13, 3620) that the silyl diazo ester 7 cyclized with high regiocontrol, inserting with retention of absolute configuration into the H adjacent to the ether oxygen. The insertion also proceeded with high diastereocontrol, to deliver an intermediate silyl lactone that was suitably arrayed for the subsequent Peterson elimination to give 8, a key intermediate for the synthesis of (+)-sundiversifolide 9. Fu-Ming Zhang and Yong-Qiang Tu of Lanzhou University prepared (J. Org. Chem. 2011, 76, 6918) the α-diazo β-keto ester 10. Rh-catalyzed intramolecular C–H insertion, again with retention of absolute configuration, gave an intermediate that on deprotection cyclized to the lactone 11, only a few steps removed from (+)-przewalskin B 12. Yikang Wu of the Shanghai Institute of Organic Chemistry devised (Org. Lett. 2011, 13, 4212) a novel preparation for cyclic peroxides such as 13. Gentle oxidation of 13 led to 14, which was further oxidized to artemisinin 15. Also known as qinghaosu, 15 is the key active component of current antimalarials.
Enantioselective Synthesis of Alcohols and Amines: The Fujii/Ohno Synthesis of (+)-Lysergic Acid
Authors: Taber Douglass F.
Published: November 2020

Ramón Gómez Arrayás and Juan C. Carretero of the Universidad Autónoma de Madrid effected (Chem. Commun. 2011, 47, 6701) enantioselective conjugate borylation of an unsaturated sulfone 1, leading to the alcohol 2. Robert E. Gawley of the University of Arkansas found (J. Am. Chem. Soc. 2011, 133, 19680) conditions for enantioselective ketone reduction that were selective enough to distinguish between the ethyl and propyl groups of 3 to give 4. Vicente Gotor of the Universidad de Oviedo used (Angew. Chem. Int. Ed. 2011, 50, 8387) an overexpressed Baeyer-Villiger monoxygenase to prepare 6 by dynamic kinetic resolution of 5. Li Deng of Brandeis University prepared (J. Am. Chem. Soc. 2011, 133, 12458) 8 in high ee by kinetic enantioselective migration of the alkene of racemic 7. Bernhard Breit of the Freiburg Institute for Advanced Studies established (J. Am. Chem. Soc. 2011, 133, 20746) the oxygenated quaternary center of 10 by the addition of benzoic acid to the allene 9. Keith R. Fandrick of Boehringer Ingelheim constructed (J. Am. Chem. Soc. 2011, 133, 10332) the oxygenated quaternary center of 13 by enantioselective addition of the propargylic nucleophile 12 to 11. Yian Shi of Colorado State University devised (J. Am. Chem. Soc. 2011, 133, 12914) conditions for the enantioselective transamination of the α-keto ester 14 to the amine 15. Professor Deng added (Adv. Synth. Catal. 2011, 353, 3123) 18 to an enone 17 to give the protected amine 19. Song Ye of the Institute of Chemistry, Beijing effected (J. Am. Chem. Soc. 2011, 133, 15894) elimination/addition of an unsaturated acid chloride 20 to give the γ-amino acid derivative 22. Frank Glorius of the Universität Münster added (Angew. Chem. Int. Ed. 2011, 50, 1410) an aldehyde 23 to 24 to give the amide 25. Sentaro Okamoto of Kanagawa University designed (J. Org. Chem. 2011, 76, 6678) an organocatalyst for the enantioselective Steglich rearrangement of 26, creating the aminated quaternary center of 27. Most impressive of all was the report (Org. Lett. 2011, 13, 5460) by Hélène Lebel of the Université de Montréal of the direct enantioselective C–H amination of 28 to give 29.
Asymmetric C–Heteroatom Bond Formation
Authors: Lambert Tristan H.
Published: November 2020

Tomislav Rovis at Colorado State University developed (Angew. Chem. Int. Ed. 2012, 51, 5904) an enantioselective catalytic cross-aza-benzoin reaction of aldehydes 1 and N-Boc imines 2. The useful α-amido ketone products 4 were configurationally stable under the reaction conditions. In the realm of asymmetric synthesis, few technologies have been as widely employed as the Ellman chiral sulfonamide auxiliary. Francisco Foubelo and Miguel Yus at the Universidad de Alicante in Spain have adapted (Chem. Commun. 2012, 48, 2543) this approach for the indium-mediated asymmetric allylation of ketimines 5, which furnished amines 6 with high diastereoselectivity. There has been vigorous research in recent years into the use of NAD(P)H surrogates, especially Hantzsch esters, for biomimetic asymmetric hydrogenations. Yong-Gui Zhou at the Chinese Academy of Sciences showed (J. Am. Chem. Soc. 2012, 134, 2442) that 9,10-dihydrophenanthridine (10) can also serve as an effective “H2” donor for the asymmetric hydrogenation of imines, including 7. Notably, 10 is used catalytically, with regeneration occurring under mild conditions via Ru(II)-based hydrogenation of the phenanthridine 11. A unique approach for asymmetric catalysis has been developed (Nature Chem. 2012, 4, 473) by Takashi Ooi at Nagoya University, who found that ion-paired complexes 14 could serve as effective chiral ligands in the Pd(II)-catalyzed allylation of α-nitrocarboxylates 12. The resulting products 13 are easily reduced to furnish α-amino acid derivatives. Another novel catalytic platform has been employed (J. Am. Chem. Soc. 2012, 134, 7321) for the chiral resolution of 1,2-diols 15 by Kian L. Tan at Boston College. Using the concept of reversible covalent binding, the catalyst 16 was found to selectively silylate a secondary hydroxyl over a primary one, thus leading to the enantioenriched products 17 and 18. Scott E. Denmark at the University of Illinois has applied (Angew. Chem. Int. Ed. 2012, 51, 3236) his chiral Lewis base strategy to the enantioselective vinylogous aldol reaction of N-silyl vinylketene imines 19 to produce γ-hydroxy-α,β-unsaturated nitriles 22. For the preparation of enantioenriched homopropargylic alcohols 25, the asymmetric addition of allenyl metal nucleophiles (e.g., 24) to aldehydes 23 provides a straightforward approach.
C–O Natural Products: (–)-Hybridalactone (Fürstner), (+)-Anthecotulide (Hodgson), (–)-Kumausallene (Tang), (±)-Communiol E (Kobayashi), (–)-Exiguolide (Scheidt), Cyanolide A (Rychnovsky)
Authors: Taber Douglass F.
Published: November 2020

Control of the absolute configuration of adjacent alkylated stereogenic centers is a classic challenge in organic synthesis. In the course of the synthesis of (–)-hybridalactone 4, Alois Fürstner of the Max-Planck-Institut Mülheim effected (J. Am. Chem. Soc. 2011, 133, 13471) catalytic enantioselective conjugate addition to the simple acceptor 1. The initial adduct, formed in 80% ee, could readily be recrystallized to high ee. In an alternative approach to high ee 2,3-dialkyl γ-lactones, David M. Hodgson of the University of Oxford cyclized (Org. Lett. 2011, 13, 5751) the alkyne 5 to an aldehyde, which was condensed with 6 to give 7. Coupling with 8 then delivered (+)-anthecotulide 9. The enantiomerically pure diol 10 is readily available from acetylacetone. Weiping Tang of the University of Wisconsin dissolved (Org. Lett. 2011, 13, 3664) the symmetry of 10 by Pd-mediated cyclocarbonylation. The conversion of the lactone 11 to (–)-kumausallene 12 was enabled by an elegant intramolecular bromoetherification. Shoji Kobayshi of the Osaka Institute of Technology developed (J. Org. Chem. 2011, 76, 7096) a powerful oxy-Favorskii rearrangement that enabled the preparation of both four-and five-membered rings with good diastereocontrol, as exemplified by the conversion of 13 to 14. With the electron-withdrawing ether oxygen adjacent to the ester carbonyl, Dibal reduction of 14 proceeded cleanly to the aldehyde. Addition of ethyl lithium followed by deprotection completed the synthesis of (±)-communiol E. En route to (–)-exiguolide 18, Karl A. Scheidt of Northwestern University showed (Angew. Chem. Int. Ed. 2011, 50, 9112) that 16 could be cyclized efficiently to 17. The cyclization may be assisted by a scaffolding effect from the dioxinone ring. Dimeric macrolides such as cyanolide A 21 are usually prepared by lactonization of the corresponding hydroxy acid. Scott D. Rychnovsky of the University of California Irvine devised (J. Am. Chem. Soc. 2011, 133, 9727) a complementary strategy, the double Sakurai dimerization of the silyl acetal 19 to 20.
Organocatalyzed Carbocyclic Construction: (+)-Roseophilin (Flynn) and (+)-Galbulin (Hong)
Authors: Taber Douglass F.
Published: November 2020

Armido Studer of Wilhems-University Münster effected (Chem. Commun. 2012, 48, 5190) the enantioselective conjugate addition of 2 to 1, leading to the cyclopropane 3. Karl Anker Jørgensen of Aarhus University devised (J. Am. Chem. Soc. 2012, 134, 2543) a route to cyclobutanes based on the enantioselective addition of 5 to the nitroalkene 4. Jose L. Vicario of the Universidad del País Vasco reported (Angew. Chem. Int. Ed. 2012, 51, 4104) a similar procedure. Benjamin List of the Max-Planck-Institute Mülheim epoxidized (Adv. Synth. Catal. 2012, 354, 1701) cyclopentenones such as 7 with high ee. Lutz H. Gade of the Universität Heidelberg observed (J. Am. Chem. Soc. 2012, 134, 2946) high ee in the benzylation of 9. Cheng Ma of Zhejiang University formylated (J. Org. Chem. 2012, 77, 2959) cyclopentanone, then condensed the resulting aldehyde 12 with 13 to give 14. Hao Xu of Georgia State University cyclized (Org. Lett. 2012, 14, 858) 15 to the cyclopentenone 16. (+)-Rosephilin 19 inhibits several phosphatases. Bernard L. Flynn of Monash University prepared (Org. Lett. 2012, 14, 1740) the carbocyclic core of 19 by cyclizing 17 to the cyclopentenone 18. Masanori Yoshida of Hokkaido University designed (J. Org. Chem. 2011, 76, 8513) a very simple organocatalyst for the enantioselective conjugate addition of 21 to 20. Samuel H. Gellman of the University of Wisconsin showed (Org. Lett. 2012, 14, 2582) that nitromethane could be added to 23 with high ee. Hiroaki Sasai of Osaka University effected (Angew. Chem. Int. Ed. 2012, 51, 5423) the enantioselective cyclization of the prochiral 25. Ying-Chun Chen of Sichuan University found (Angew. Chem. Int. Ed. 2012, 51, 4401) that the diene 27 could be converted to 29 by way of the intermediate trienamine. Bor-Cherng Hong of the National Chung Cheng University observed (Chem. Commun. 2012, 48, 2385) that under organocatalysis, only one enantiomer of 31 would add to 30, delivering 32 in high ee. Aromatization of 32 led to (+)-galbulin 33.
Diels-Alder Cycloaddition: Fawcettimine (Williams), Apiosporic Acid (Helmchen), Marginatone (Abad- Somovilla), Okilactomycin (Hoye), Vinigrol (Barriault), Plakotenin (Bihlmeier/Klopper)
Authors: Taber Douglass F.
Published: November 2020

Highly substituted dienes and dienophiles are often reluctant participants in intermolecular Diels-Alder cycloaddition. Nevertheless, Robert M. Williams of Colorado State University, in the course of a synthesis of fawcettimine 4, was able (J. Org. Chem. 2012, 77, 4801) to prepare 3 by combining the enone 1 with the diene 2. Günter Helmchen of the Universität Heidelberg set (J. Org. Chem. 2012, 77, 4491) the single stereogenic center of 5 by Ir-catalyzed allylic alkylation. The Lewis acid that promoted the cycloaddition also conveniently removed the trityl protecting group, leading to 6, that was saponified to apiosporic acid 7. Antonio Abad-Somovilla of the Universidad de Valencia prepared (J. Org. Chem. 2012, 77, 5664) the triene 8 in enantiomerically pure form from carvone. Despite the additional substitution on the diene, cycloaddition proceeded smoothly to give 9, which was carried on to marginatone 10. One could envision that okilactomycin 13 could be formed by an intramolecular Diels-Alder cycloaddition. Thomas R. Hoye of the University of Minnesota observed (Org. Lett. 2012, 14, 828) that the tetraene tetronic acid corresponding to 11 was inert, but that the methyl ether 11 cyclized smoothly to 12. Demethylation then gave the natural product The complex polycyclic structure of vinigrol 16 challenged organic synthesis chemists for many years, until a route was established by Phil Baran of Scripps/La Jolla (Highlights September 6, 2010). Louis Barriault cyclized (Angew. Chem. Int. Ed. 2012, 51, 2111) 14 to 15 en route to a late intermediate in the Baran synthesis It had been hypothesized that the natural product plakotenin 19 was formed naturally from a tetraene corresponding to 17. The tetraene 17 was prepared and the cyclization was successful, “confirming” both the structure of the natural product and the biosynthetic hypothesis. Angela Bihlmeier and Wim Klopper of the Karlsruhe Institute of Technology calculated (J. Am. Chem. Soc. 2012, 134, 2154) the relative energies of the four competing transition states for the cyclization, leading to a correction of the structure of 18, and so of the natural product 19.
The Carreira Synthesis of (+)-Daphmanidin E
Authors: Taber Douglass F.
Published: November 2020

(+)-Daphmanidin E 3, isolated from the leaves of Daphniphyllum teijsmanni, shows moderate vasorelaxant activity on the rat aorta. Considering the curiously compact structure of 3, Erick M. Carreira of ETH Zürich chose (Angew. Chem. Int. Ed. 2011, 50, 11501) to start the synthesis from the enantiomerically pure bicyclic diketone 2. The mono enolate of 2 was readily prepared, but the steric bulk of the ketal of 4 was needed to direct the subsequent hydroboration. Indeed, the alkene of 5 was so congested that excess BH3 at elevated temperature was required. Under those conditions, the esters were also partially reduced, so the reduction was completed with Dibal to deliver the crystalline triol 6. After protection of the alcohols, the remaining carbon atoms of 3 were added by sequential Claisen rearrangements. O-Alkylation with 7 delivered 8, which rearranged with 10:1 diastereoselectivity. After O-allylation, the second Claisen rearrangement led to 9 as the only isolable product. Selective hydroboration of 9 led to 10, which was deprotected, then dehydrated following the Grieco protocol. Functional group manipulation of 11 led to the aldehyde 12, which was condensed with nitromethane to give 13. Direct conjugate addition to 13 gave at best a 1:3 preference for the wrong diastereomer. With a chiral Cu catalyst, this was improved to 5:1 in favor of the desired diastereomer. Ozonolysis of 14 followed by selective reduction of the aldehyde gave the primary alcohol, which was carried onto the iodide. Elimination with DBU then delivered 15, setting the stage for the key intramolecular bond connection. After extensive exploration, it was found that irradiation of 15 in the presence of a catalytic amount of a cobaloxime catalyst and a stoichiometric amount of Hünig’s base gave clean cyclization to 16. The last carbocyclic ring of (+)-daphmanidin E 3 was closed by intramolecular aldol addition of the aldehyde of 17 to the ketone, followed by dehydration. The seemingly simple intramolecular imine formation to prepare the natural product, initially elusive, was effected by heating the ammonium salt in ethanol. The Co-catalyzed cyclization of 15 to 16 is particularly striking.
The Li Synthesis of (–)-Fusarisetin A
Authors: Taber Douglass F.
Published: November 2020

Fusarisetin A 3 is an intriguing inhibitor of cell migration and invasion that is not itself cytotoxic. Ang Li of the Shanghai Institute of Organic Chemistry developed (J. Am. Chem. Soc. 2012, 134, 920) a total synthesis of (–)-fusarisetin A, demonstrating that the natural material had the absolute configuration opposite to that originally assigned. A key step in the synthesis was the highly diastereoselective cyclization of 1 to 2. The absolute configuration of 1 and so of synthetic 3 was derived from commercial citronellol, which is prepared on an industrial scale by asymmetric synthesis. To this end, the reagents 6 and 8 were required. The β-ketothio ester 6 was prepared from the Meldrum’s acid 4 and the phosphonate 8 was derived from methyl sorbate 7. The acetal of citronellal 9 was ozonized with reductive work-up to give the alcohol 10. Protection followed by hydrolysis gave the aldehyde 11, which was condensed with 8 to give the triene 12. Deprotection followed by oxidation delivered an aldehyde, which was condensed with 6 to give the Diels-Alder precursor 1. With BF3 • OEt2 catalysis, the Diels-Alder cycloaddition proceeded under mild conditions, –40oC for 40 min, leading to 2 as a single diastereomer. Comparable intramolecular Diels-Alder cyclizations with single carbonyl activation gave mixtures of diastereomers. The alcohol 13 was prepared by transesterification of 2 with trifluoroethanol. Activation with MsCl led directly to the kinetic O-alkylation product 14. Following the precedent of Trost (J. Am. Chem. Soc. 1980, 102, 2840), exposure to a Pd catalyst smoothly converted 14 into 15 as the desired diastereomer. Condensation of the ester 15 with the amine 16 gave the diene 17. Selective oxidation of the monosubstituted alkene under Wacker conditions gave the ketone, which was reduced selectively by the Luche protocol to the alcohol 18. Exposure of 18 to NaOCH3 initiated Dieckmann cyclization, leading to (–)-fusarisetin A 3.
The Vanderwal Synthesis of Echinopine B
Authors: Taber Douglass F.
Published: November 2020

Intramolecular cyclopropanation has long been a powerful strategy for stereoselective polycarbocyclic construction. For many years, this was limited to diazo carbonyl insertion. More recently, alternative strategies for intramolecular cyclopropane construction have been developed. The power of such an approach is illustrated by the total synthesis of echinopine B 3 reported (Angew. Chem. Int. Ed. 2012, 51, 7572) by Christopher D. Vanderwal of the University of California, Irvine. The starting material for the synthesis was the commercial keto ester 4. Enol ether formation followed by cyclopropanation set the stage for fragmentation to the enone 7. The cyclopentannulation reagent 9 was prepared in two steps from butynol 8. Following the precedent of Heathcock (J. Am. Chem. Soc. 1983, 105, 2354), conjugate addition proceeded with significant diastereocontrol to give the ketone 10. Exposure of the derived tosylate to less than one equivalent of lithium diisopropylamide gave clean cyclization to the bicyclic ketone 11. It is a measure of the brevity of this approach that the cyclization of 10 to 11 was reported on a 5-gram scale. Relatively little is known about conformational preference around seven-membered rings. Methylenation of 12 followed by reduction of the ester delivered the aldehyde 13. Epimerization of the aldehyde with methanolic K2CO3 gave a 4:1 mixture, with the new aldehyde dominating. Inclusion of the Ohira reagent 13 in the same pot with 11 gave the alkyne 15, also as an ~4:1 mixture of diastereomers. Alkylation with MOM-Cl then completed the assembly of 1. Warming of 1 with a catalytic amount of PtCl2 led to the cyclopropane 2. This reaction apparently proceeded through a series of steps leading to a Pt carbene that then underwent β-hydride elimination to give the enol ether. On oxidation, the enol ether was smoothly converted to the methyl ester, echinopine B 3 In this synthesis, the targeted natural product included a cyclopropane. Fused cyclopropanes are also versatile precursors to other polycyclic ring systems. Future developments in intramolecular cyclopropane construction will open efficient new strategies for polyalicyclic synthesis.
The Carreira Synthesis of (±)-Gelsemoxonine
Authors: Taber Douglass F.
Published: November 2020

The traditional Chinese pharmacopeia includes Gelsemium elegans benth, from which the alkaloid gelsemoxonine 3 was isolated. Erick M. Carreira of the Eidgenössische Technische Hochschule Zürich envisioned (J. Am. Chem. Soc. 2013, 135, 8500) that the unusual azetidine ring of 3 could be established by Brandi contraction of 1 to give 2. Following Brandi and Salaün (Eur. J. Org. Chem. 1999, 2725), the hemiketal 4 was carried onto the aldehyde 9. Condensation with nitromethane followed by dehydration gave the unsaturated nitrile oxide, which cyclized to 10. Epoxidation of 10 across the more open face gave an intermediate epoxide. Addition of 11 to the epoxide, promoted by InBr3, delivered 12 with good stereocontrol. CeCl3-mediated addition of 1-propynyl lithium completed the assembly of 1. A cyclopropanone could be seen as the addition product of carbon monoxide to an alkene. On exposure of 1 to acid, this formal addition was reversed, leading to the β-lactam 2. A computational study of this cleavage was recently reported (Eur. J. Org. Chem. 2011, 5608). Conceptually, one can imagine protonation activating the C–N bond for cleavage, leading to an intermediate such as 14, which then fragments to the acylium ion, leading to cyclization. It is unlikely that 14 would have any real lifetime. On warming with the Petasis reagent, the Boc-protected β-lactam was converted to the alkene 15. Hydroboration proceeded to give the alcohol 16 as a single diastereomer. Reduction followed by oxidation to 17 then set the stage for intramolecular aldol condensation to give 18. The last challenge was the diastereoselective assembly of the N-methoxyoxindole. To this end, oxidation and dehydration of 18 led to the bromo amide 20. As hoped, Heck reductive cyclization proceeded across the more open face of the alkene, leading to 21. Hydroxyl-directed hydrosilylation of the pendant alkyne to give the ethyl ketone then completed the synthesis of gelsemoxonine 3. Twice in this synthesis, advantage was taken of the preparation and reactivity of heteroatom-substituted alkenes. Dimethyl dioxirane, generated as a solution in acetone, was sufficiently water free that the epoxide derived from 10 could survive long enough to react in a bimolecular sense with the ketene silyl acetal 11.
Pyrite and the Global Environment
Authors: Rickard David
Published: November 2020

The two basic processes concerning pyrite in the environment are the formation of pyrite, which usually involves reduction of sulfate to sulfide, and the destruction of pyrite, which usually involves oxidation of sulfide to sulfate. On an ideal planet these two processes might be exactly balanced. But pyrite is buried in sediments sometimes for hundreds of millions of years, and the sulfur in this buried pyrite is removed from the system, so the balance is disturbed. The lack of balance between sulfide oxidation and sulfate reduction powers a global dynamic cycle for sulfur. This would be complex enough if this were the whole story. However, as we have seen, both the reduction and oxidation arms of the global cycle are essentially biological—specifically microbiological—processes. This means that there is an intrinsic link between the sulfur cycle and life on Earth. In this chapter, we examine the central role that pyrite plays, and has played, in determining the surface environment of the planet. In doing so we reveal how pyrite, the humble iron sulfide mineral, is a key component of maintaining and developing life on Earth. In Chapter 4 we concluded that Mother Nature must be particularly fond of pyrite framboids: a thousand billion of these microscopic raspberry-like spheres are formed in sediments every second. If we translate this into sulfur production, some 60 million tons of sulfur is buried as pyrite in sediments each year. But this is only a fraction of the total amount of sulfide produced every year by sulfate-reducing bacteria. In 1982 the Danish geomicrobiologist Bo Barker Jørgensen discovered that as much as 90% of the sulfide produced by sulfate-reducing bacteria was rapidly reoxidized by sulfur-oxidizing microorganisms. Sulfate-reducing microorganisms actually produce about 300 million tons of sulfur each year, but about 240 million tons is reoxidized. The magnitude of the sulfide production by sulfate-reducing bacte­ria can be appreciated by comparison with the sulfur produced by volcanoes. As discussed in Chapter 5, it was previously supposed that all sulfur, and thus pyrite, had a volcanic origin. In fact volcanoes produce just 10 million tons of sulfur each year.
The Council on Environmental Quality: 1970–2010
Authors: Conant James K. , Balint Peter J.
Published: November 2020

On January 1, 1970, President Richard Nixon signed the National Environmental Policy Act of 1969 (NEPA) into law. In this Act, Congress articulated for the first time a national policy on the environment. The goals of the Act included the promotion of “efforts to prevent or eliminate damage to the environment and biosphere and stimulate the health and welfare of man.” Congress also created the Council on Environment Quality (CEQ) to assist the president with the implementation of the new law and placed the new agency in the Executive Office of the President. The CEQ was to consist of three members, and it was to be supported by a professional staff selected by the CEQ. On January 29, 1970, President Nixon nominated Russell E. Train to serve as the chair of the CEQ; he also nominated Robert Cahn and Gordon J. F. MacDonald to serve as the other members of the CEQ. One week later, on February 6, 1970, the Senate confirmed the nominations, which officially allowed the new agency to open for business. In addition to ongoing consultations with the president and his advisors, Chairman Train and the other two members of the CEQ had to assemble a professional and administrative staff. In August of 1970, only six months after the CEQ officially opened for business, President Nixon submitted The First Annual Report of The Council on Environmental Quality to Congress. The front section of the Report was “The President’s Message to Congress.” The remainder of the Report, developed by the CEQ, contained the first assessment of the nation’s environment, a list of the underlying causes and effects of existing environmental problems, a review of the national government’s efforts to address those problems over the previous two decades, and recommendations for improving environmental quality and protecting human health that involved changes in policy and administrative structure. It is especially noteworthy that the Report contained a section on the causes and effects of climate change, as well as recommendations for addressing this critical problem. In this chapter, we describe and attempt to explain what has happened to the CEQ over the forty-year period from 1970 to 2010.
Postscript: Sustainability and the Environmental Protection Agency
Authors: Conant James K. , Balint Peter J.
Published: November 2020

In Chapter 7, we completed our formal examination of environmental politics, policy, and administration. In our analysis throughout the book we examined the histories of the Council on Environmental Quality (CEQ) and the Environmental Protection Agency (EPA) as seen through the lens of conceptual agency life cycle models. In this postscript, we step outside this theoretical framework to offer some thoughts on the path U.S. environmental policy and administration have been taking, in halting steps, toward the ambitious processes and goals of sustainability. In considering the practical implications of this emerging realignment of focus, we use climate change as an example. As we discussed in Chapter 2, the National Environmental Policy Act of 1969 (NEPA) was a prescient document helping chart new directions in environmental management both in the United States and globally. Although NEPA does not specifically mention sustainability, the act includes text that clearly anticipates current understanding of the concept, declaring it a policy of the federal government “to create and maintain conditions under which man and nature can exist in productive harmony, and fulfill the social, economic, and other requirements of present and future generations of Americans.” In 1987 the United Nations World Commission on Environment and Development built on this language to define sustainable development as “development that meets the needs of the present without compromising the ability of future generations to meet their own needs.” At the 1992 Earth Summit, 178 nations committed to adopting this framework in promoting future development. While this declaration, known as Agenda 21, did not immediately transform global priorities, it did put sustainability on the international agenda. Since then, the Organisation for Economic Co-operation and Development (OECD), a multilateral group of thirty-four nations made up primarily of developed economies, has been particularly active in encouraging member countries to incorporate sustainability into policymaking. Over the past decade or so, sustainability has become a more visible part of the vocabulary of U.S. environmental policy and administration.
Changes in Washington Affect the DDT Battle
Authors: Wurster Charles F.
Published: November 2020

Late in 1970, President Nixon proposed and Congress approved creation of the Environmental Protection Agency (EPA), in the process transferring the Pesticide Regulation Division from USDA to EPA. For pesticide regulation, this was no minor matter. The transfer was from USDA, an agency that primarily protected pesticide manufacturers and promoted their products, to EPA, an agency that was directly charged with protecting the environment. That was to make a large difference in how the DDT issue would be resolved. The first administrator of EPA was William D. Ruckelshaus, an attorney with a sterling record of public service in government. The other major item was the decision on DDT from the DC Court of Appeals. On January 7, 1971, the court ordered Ruckelshaus to immediately cancel all registrations of DDT and to determine whether DDT was “an imminent hazard to the public” and therefore should be suspended. The court was clearly annoyed by USDA’s failure to give adequate reasons for not suspending, so “it will be necessary to remand the case once more, for a fresh determination” of the matter of suspension. The court had taken away the discretion usually afforded a federal agency and ordered it to take action. This was an unprecedented decision. EPA had only been created on December 2, 1970; Ruckelshaus barely had time to find his telephone before this court order landed on his desk as his first order of business. Perhaps the most important part of this decision was that EDF survived USDA’s motions to throw our case out of court. The standing for citizens to sue the government, previously unavailable, had now been established by this precedent-setting decision. This was the firm beginning of what we now call “environmental law.” But you should not take the legal conclusion of a lowly scientist (me). Instead, here are the words of Joseph L. Sax, a professor of law at the University of Michigan Law School, from his September 30, 1973, letter in support of EDF’s application for the Tyler Ecology Award (we did not get it).
Strangled Waters: Second Wave
Authors: Levy Sharon
Published: November 2020

In August 2014, the water supply for the city of Toledo, Ohio, was poisoned. Officials issued an order to the half- million residents connected to the municipal water supply: Don’t drink, cook, or brush your teeth with the water. Do not use it to bathe your children, and don’t give it to your pets. Stores ran out of bottled water, and residents had to wait in long lines or travel to neighboring towns to find more. The culprit was a bright green plume of Microcystis, a cyanobacterium that thrives in warm water tainted with heavy loads of phosphorus and nitrogen. Every spring, rains wash a pulse of nutrients off fertilized fields and send it down the Maumee and Sandusky rivers and into western Lake Erie. Every summer, as water temperatures rise, Microcystis forms an iridescent mat over parts of the lake’s surface. In early August 2014, strong winds blew a lawn of cyanobacteria over Toledo’s water intake, which lies just outside the Maumee’s mouth. Tests showed that the city’s water contained dangerous levels of microcystin, a liver toxin produced by the bloom. The drinking water crisis was a dramatic signal of Lake Erie’s descent back into eutrophication. In the 1980s, after sewage plants in the watershed were upgraded and phosphate detergents banned, Lake Erie experienced a revival. Algal blooms faded, and populations of walleye rebounded. The lake grew a thriving tourist industry based on sport fishing. Then, in 1995, researchers recorded the lake’s first wide­spread bloom of Microcystis. Eruptions of Microcystis have since become a predictable event striking the western Lake Erie basin every summer. The most widespread and long- lasting blooms hit in 2011 and 2015, after intense spring rains dumped heavy loads of nutrients into the lake. Climate models forecast warmer summer temperatures and heavier spring rains for the Great Lakes region. Those conditions are a recipe for more and larger algal blooms, and are likely to favor Microcystis in particular. The regulatory efforts of the 1970s and 1980s made great progress in cleaning up discharges from industries and sewage treatment plants, but failed to address nonpoint source pollution flowing from farm fields and city streets.
Territorial Integrity
Authors: Toal Gerard
Published: November 2020

On the Evening of August 7, 2008, Inal Pliyev was working late at his office in the center of Tskhinval(i). A former journalist, Pliyev was head of communications for the self-declared South Ossetian Republic. Earlier in the evening, Georgian president Mikheil Saakashvili had declared a unilateral ceasefire after days of skirmishes between Georgian forces and South Ossetian militias. Pliyev, however, was still in the office because of information about increasing Georgian artillery and armor concentrations near the town. “First we heard what sounded like grenade launchers—after the years of conflict everyone here knows what sound is made by which weapon. I did not pay much attention to that.” But when he heard the first sounds of Grad missiles, Pliyev turned off his computer and ran for his life. “All parts of the city came under fire simultaneously. It was so intense, that you couldn’t even register a fraction of time between explosions, there were multiple explosions every second. The fire was non-stop. Electricity and gas supplies were cut off during the first minute of the shelling, and for the most part phone service was also cut off.” One shell fell next to the government building where Pliyev and his colleagues huddled. “The building shook so much that part of the ceiling bent down, and we ran into an underground bunker in a nearby non-government building. Explosions were becoming louder and even more frequent. We could not leave our hideout, and everyone was getting ready to die. Even more we feared being taken prisoner by Georgian soldiers. It was especially terrifying when we heard machine gun fire. Our only thought was to avoid being taken prisoner at any cost. Our only hope was for the Russian air force, we were waiting for it to come, so that Georgians would leave our city. But it wasn’t coming.” Pliyev had his mobile phone, and as its battery ran out he spoke to various Russian media outlets pleading for Russian military help.
Long-Term Planning and Legal Issues
Authors: Ellis Michael
Published: November 2020

Please be aware that I am not an attorney and the following information should not be considered legal advice. The information contained in this chapter is what I have learned as a parent of a child with autism spectrum disorder (ASD) and as a doctor trying to help those with ASD navigate complex legal and financial decisions. I recommend all parents of children with ASD develop a relationship with a licensed attorney with experience in special needs in their jurisdiction. As this chapter details, there are many different legal issues you and your child may encounter as your child matures into adulthood. Having an attorney who is familiar with your specific situation and your child can be very reassuring should legal needs arise. If you have the financial capacity to place some funds in a retainer with an attorney so that they are available any time you need for a quick e-mail, phone call, or text message, it is often worth the expense and peace of mind. Parents can usually locate attorneys with experience in special needs by contacting their local bar associations, many of which maintain formal referral programs. Also, many autism support groups maintain lists of attorneys who specialize in various aspects of the law relevant to children with ASD. Your child’s medical providers may also be able to provide referrals. If you are like most parents of a child with ASD, you are over­whelmed with even the thought of long-term planning. You are likely thinking, “It is hard enough making it day by day, let alone considering long-term planning.” The truth is that most of us avoid thinking of the future because it is too frightening and uncertain. There is also little guidance from healthcare professionals on this very complex issue. However, much relief can be found in achieving a plan for your child’s future. Do not wait. It is important to talk with a financial planner when your child is young.
Romans, Mayans, and Anasazi: The Classical Optimum to Droughts in the Americas
Authors: McMichael Anthony
Published: November 2020

The Stories of the Roman Empire and the Mayans are well known and have fascinated generations of scholars, artists, storytellers, and his­tory enthusiasts. Less familiar are the ways in which the changing climate contributed to the rise and fall of these civilizations, and of the Anasazi, among others in North America. This chapter examines the fates of differ­ent societies in three climatic periods: the warm Classical Optimum (300 B.C.E. to 350 C.E.), cooler conditions in the Dark Ages (500 C.E. to 800 C.E.), and drought in the Americas (950 C.E. to 1250 C.E.). Recent gains in the reach and resolution of paleoclimatology have enabled more detailed reconstruction of climate and health relationships. Beginning around 300 B.C.E., Europe and the Mediterranean experienced a prolonged period of warm and stable climate—often termed the Roman Warm. Historian John L. Brooke has labeled the ensuing “remarkable” 600 to 800 years of benevolent climate conditions the Classical Optimum, and he suggests that the effects were global. A positive North Atlantic Oscillation (NAO) pushed warm winds west towards Scandinavia, glaciers retreated, and the Mediterranean settled into its characteristic pattern of dry summers and winter rainfall. In the wake of the spread of farming and rising fertil­ity rates, the estimated global population was approaching 200 million. Cities were becoming larger and grander, trade routes were extending, and armies and their iron weaponry were ranging further afield. So too were various infectious agents, many of them beneficiaries of the new and intensifying transcontinental contacts among China, Rome, South Asia, the Middle East, and North and East Africa. During this period, the Mediterranean sustained “the deepest land­scape transformation in antiquity.” Scattered populations increased and coalesced into forts and cities, supported by thousands of new farms. By around 300 C.E., however, the Classical Optimum began to wane. Ice- melt events cooled northern Europe, and by 500 C.E. the strong NAO reversed, bringing a deep cold. The shifting climatic con­ditions placed enormous pressure on the civilizations that had trans­formed their socio- ecological systems during conditions more favourable to agricultural productivity and human health.
Humans throughout the Holocene
Authors: McMichael Anthony
Published: November 2020

What Does the Story about human experiences of past natural cli­matic changes tell us in broad terms? At the least it points to the types of risks to the health, survival, and social stability of diverse populations likely to result from this century’s human- driven climate change. This chapter and the next look to that future, and to how humankind might avert the looming environmental and social crises. In preparation, pa­leoclimatologist Raymond Bradley argues that we should seek “insight into the nature and magnitude of past regional [climatic] anomalies and their human impacts by examining the Holocene paleoclimate record.” This chapter asks whether there are discernible patterns in the long story of past climate change and population health adversity. Have particular conditions and factors determined vulnerability to those ad­verse impacts? On this basis, how vulnerable are today’s populations, rich and poor, tropical and polar, to the climatic stressors and associ­ated risks anticipated in this twenty- first century? An overview of the Holocene’s 11,000- year climatic experience, a mere sliver of the total Homo sapiens experience of climate variation, provides a good entry point. This latest of the nine interglacial periods during the past million years has been the one in which anatomically and behaviorally modern humans began exerting increasing control over the environment and its carrying capacity by shifting toward growing crops, herding animals, managing water flows, and building settlements. That agriculturally based era is shown near the top right in Figure 10.1, a moment in geological time. Throughout the Holocene, the climate was, as ever, naturally variable, and the gods of rain, sun, wind, and warmth held great sway over harvests, hunger, and viability. We will summarize here the main points from earlier chapters as the basis for a discussion of patterns in the past which may point to future vulnerability and implications for human well- being. The Holocene has been a period of relative climatic constancy, with an average global surface temperature of 15oC Changes in temperature and rainfall spanning several centuries have occurred, as have many shorter- term fluctuations.
The Silver Bullet
Authors: Lupia Arthur
Published: November 2020

People express different opinions about what types of information and knowledge others should have. They offer lists of names, institutional characteristics, or historical facts that are claimed to be essential for competent citizenship. One difficulty facing people who make such claims is that there are thousands of such lists in circulation—and these lists of “what others should know” tend not to look alike. For example, some people make arguments about what others should know in an openly ideological manner—asserting that certain facts and values with which they agree are what everyone should know—and actively think about—when making particular decisions. In the debate over the legal status of abortion, for example, pro-life participants implore others to elevate information about the fetus over other available claims, while pro-choice participants seek to elevate information about the pregnant woman’s well-being over other available claims. Participants in these debates regularly disagree about what kinds of information and knowledge are needed for people to make “competent” decisions about abortion’s legal status. At this point in the book’s discussion of the relationship among information, knowledge, and competence, I want to tell you about a question that I am sometimes asked when giving presentations on these topics. The question is “What do people really need to know about politics (or government or science or climate or “Obamacare,” etc.)?” Many people who ask this question believe it to be a simple one that is answerable in just a few words. In these instances, I am being asked to produce a silver bullet. What is a silver bullet? In folklore, a silver bullet is a device that defeats many different types of monsters (such as werewolves and witches). Today, it refers to a simple solution to a complex problem. The silver bullet that people seek from me is a short set of “facts” that, if only everyone knew them, would guarantee a basic level of competence in tasks such as voting. My questioners are seeking a one-size-fits-all informational solution to a competence concern about which they care deeply.
Value Diversity and How to Manage It
Authors: Lupia Arthur
Published: November 2020

Value diversity causes people to give different answers to questions like “What information is most valuable to convey?” and “Who needs to know what?” I define values as do Shalom Schwartz and Wolfgang Bilsky (1987: 551). By values, they mean “(a) concepts or beliefs, (b) about desirable end states or behaviors, (c) that transcend specific situations, (d) guide selection or evaluation of behavior and events, and (e) are ordered by relative importance.” By value diversity, I refer to the different values that people have. This chapter is about how value diversity affects claims about what is worth knowing and, hence, an educator’s ability to get prospective learners and supporters to participate in an educational endeavor. Some critics and educators regard values as a nuisance— particularly the values of those with whom they disagree. These critics want people to teach a particular set of conclusions about a subject that matters to them. They often see others’ values as illegitimate and as getting in the way of a rational conversation about issues that they consider important. These claims manifest as advice for others to focus on “just the facts.” I will show that these critiques often reflect a misunderstanding of how values affect learning. I will also show how to overcome these misunderstandings in ways that enhance educators’ abilities to increase many kinds of knowledge and competence. . . . Here is a short summary of the chapter’s main conclusions: Values affect how people perceive and process information. Values drive individuals to embrace certain types of information and reject others. Values often have these effects before prospective learners are conscious of them, and they have these effects even if prospective learners have trouble describing them. . . . In other words, values affect the types of information prospective learners are willing to pay attention to and regard as credible. As attention and credibility are critical assets for educators to possess, and as political situations often include people with different values, educators who understand how values affect learning can make more effective choices about what information to convey.