bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthese von 3‐(2‐Carboxy‐4‐Pyridyl)‐ und 3‐(6‐Carboxy‐3‐pyridyl)‐DL‐alanin
Authors: Hilpert Hans 
Published: December 2004

Synthesis of 3‐(2‐Carboxy‐4‐pyridyl)‐and 3‐(6‐Carboxy‐3‐pyridyl)‐DL‐alanineAs starting materials for potential photochemical approaches to betalaines C(R = COOH) and to muscaflavine F(R = COOH), β‐(2‐carboxy‐4‐pyridyl)‐ and β‐(6(carboxy‐3‐pyridyl))‐DL‐alanine (A and D with R = COOH or 4 and 11), respectively, were prepared (Scheme 1). The synthesis of 4 (= A, R = COOH) started with the 2‐[(4‐pyridyl)methyl]malonate 1 and proceeded via the N‐oxide 2, cyanation and hydrolysis (Scheme 2). Amino acid 11 was obtained from (3‐pyridyl)methyl‐bromide (6) via the malonate 7 by an analogous sequence of reactions (Scheme 3).
Glycosylphosphonates of 2‐Amino‐2‐deoxy‐aldoses. Synthesis of a Phosphonate Analogue of Lipid X
Authors: Briner Karin , Vasella Andrea 
Published: December 2004

AbstractA preparation of glycosylphosphonates (27, 28, 36, 38, and 39) from 2‐azido‐2‐deoxy‐glycoses (26,35, and 37) and the synthesis of the non‐isosteric phosphonate analogue 3a of lipid X(2) are described. The 2‐azido group was introduced by azidonitration. Treatment of the 1‐O‐acetyl‐2‐azido‐2‐deoxy‐β‐D‐galactopyranose 22 with 1.5‐3 equiv. of P(OMe)3 and 1.2‐2.5 equiv. of TfOSiMe3 gave mainly recovered starting material. In P(OMe)3 as the solvent, the dimethyl phosphoramidate 24 was obtained by way of a Staudinger reaction, even in the presence of TfOSiMe3. Treatment of the benzylated α‐D‐galacto‐trichloroacetimidate 26, however, with P(OMe)3 and TfOSiMe3 gave a 1:1 mixture of the α‐ and β‐D‐galacto‐phosphonates 27 and 28, while the acetylated α‐D‐gluco‐ imidate 35 led to the α‐D‐gluco‐configurated phosphonate 36. The stereoselectivity of the phosphonate formation is related to the relative ease of formation of oxonium‐ion intermediates from 26 and 35. Starting from the phosphonate 36, deacetylation, benzylidenation, reduction of the azido group, acylation with (R)‐3‐(benzyloxy)tetradecanoic acid and deprotection yielded the desired compound 3a which was crystallized in the presence of 2 equiv. of (aminomethylidyne)trimethanol (Tris.). The structure of the phosphonates was deduced from their 1H‐, 13C‐, and 31P‐NMR spectra.
Cyclopentenone Annulation of 2‐Oxocycloalkane‐1‐carbonitriles
Authors: Vassil I. Ognyanov , Hesse Manfred 
Published: December 2004

AbstractPhase‐transfer alkylation of the 2‐oxocycloalkane‐l‐carbonitriles 1a and 1b with ethyl 4‐bromo‐3‐methoxy‐2‐butenoate (2), followed by deprotection and base‐catalyzed cyclization gave the annulated cyclopentenones 5a and 5b, respectively, in high overall yields (Scheme 1). Stereoselective catalytic hydrogenation of 5b followed by de‐ethoxycarbonylation afforded 14‐oxo‐cis‐bicyclo[10.3.0]pentadecane‐l‐carbonitrile (7). Treatment of 7 with LiN(i‐Pr)2 in THF gave the known synthetic muscone precursor 8 (Scheme 2). The tricyclo[10.4.0.01,15]hexadecan‐14‐one (14) was prepared from 7 in 5 steps by a reaction sequence proceeding without affecting the chiral centres (Scheme 2). The structure of 14 was established by X‐ray structure analysis (Figure).
MNDO Analysis of Regio‐ and Stereoselectivity in Hydroboration
Authors: Egger Martin , Keese Reinhard 
Published: December 2004

AbstractThe origin of regioselectivity in hydroboration of olefins has been analyzed by MNDO methodology. With a standard transition structure derived from full MNDO optimizations, a linear correlation between calculated and experimental regioselectivities has been found. A similar approach applied to asymmetric inductions of hydroboration with chiral hydroborating agents lead also to an acceptable linear correlation between calculated and experimental results. The MNDO method has been used for a search of alternative hydroborating agents.
Alkylation of Imidazolidinone Dipeptide Derivatives: Preparation of Enantiomerically Pure Di‐ and Tripeptides by ‘Chirality Transfer’ via a Pivalaldehyde N,N‐Acetal Center. Preliminary Communication
Authors: Polt Robin , Seebach Dieter 
Published: December 2004

AbstractGlycylglycine, glycyl‐(S)‐alanine, and (S)‐alanylglycine esters are cyclized through pivalaldehyde imines to give dipeptide‐derived 3‐(benzyloxycarbonyl)‐2‐(tert‐butyl)‐5‐oxoimidazolidine‐1‐acetates 1–3. These are alkylated diastereoselectively by Li‐enolate formation and addition of alkyl bromides or iodides (products 4–6). Starting from (S)‐alanine and glycine, (S)‐alanyl‐(S)‐alanine or (R)‐alanyl‐(R)‐alanine, and (R)‐alanyl‐(R)alanyl‐(S)‐alanine‐ have thus been prepared, with the (tert‐butyl)‐substituted N,N‐acetal center playing the role of a pivot or lever for diastereoselective formation of new stereogenic centers under kinetic or thermodynamic control.
EPC‐Synthesis of Tetrahydroisoquinolines by Diastereoselective Alkylation at the 1‐Position of Phenylalanine‐Derived Precursors. Synthesis of the Alkaloid (+)‐Corlumine
Authors: Huber Isabelle M. P. , Seebach Dieter 
Published: December 2004

AbstractThe 1,2,3,4‐tetrahydro‐N‐pivaloyl‐isoquinoline‐3‐carboxylic acids1d,2d, and3d, derived from (R)‐ or (S)‐phenylalanine, (S)‐dopa, and (S)‐α‐methyldopa, respectively, are doubly deprotonated with (tert‐butyl)lithium in THF and alkylated at the 1‐position (products5–10). The major diastereoisomers formed are the result of electrophilic attack from the face opposite to the carboxylate group (rel. topicityul‐1,3). Even the addition to benzaldehyd (→7,8) is highly stereoselective (oneof four diastereoisomers is formed exclusively (300‐MHz1H‐NMR analysis)), if MgBr2etherate is added prior to the electrophile. Some of the obtained amino‐acid derivatives are decarboxylated by anodic oxidation inMeOH(→11,12,17) and NaBH3CN reduction, and converted to the known 1‐methyl‐ and 1‐benzyltetrahydroisoquinolines (15,16) of > 95% ee as well as to the phthalide isoquinoline alkaloid (+)‐corlumine of ≥80% ee. The synthetic approach described here is compared with other methods of synthesizing enantiomerically pure 1‐substituted tetrahydroisoquinolines (and thus an important group of alkaloids,Scheme 1).
Adriadysiolide, the First Monoterpenoid Isolated from a Marine Sponge
Authors: Mancini Ines , Guella Graziano , Guerriero Antonio , Boldrin Alfredo , Pietra Francesco 
Published: December 2004

AbstractSpectra and chemical transformations allow to establish the gross structure 6,7‐epoxy‐4,7‐dimethyl‐l‐oxa‐spiro[4.4]non‐3‐en‐2‐one for adriadysiolide (1), the first monoterpenoid isolated from a marine sponge, a Dysidea sp. of the Adriatic Sea. Its configuration 5R*, 6S*, 7S* as given in 1a is derived from diastereoselective total syntheses of both 1a and its diastereoisomer 1b via stereochemically predictable peracid epoxidations of olefinic precursors. Thus, OH assistance in allylic alcohol 8 leads to oxirane 13 which is subjected to methyl cuprate conjugate addition to give epiadriadysiolide (1b), whilst electronic deactivation by a neighboring heterocyclic O‐atom in intermediate 5, derived from 8 mainly leads to adriadysiolide (1a). Comparative 1H‐NMR shift‐reagent effects with 1a and 1b, evaluated with the aid of molecular‐mechanics calculations, support these conclusions.
17O‐NMR Spectra of Cyclopropenones and Tropone. Oxygen Exchange with Water
Authors: Dahn Hans , Ung‐Truong My‐Ngoc 
Published: December 2004

AbstractWhereas tropone (2) and a cyclopropanone 5 show rather normal ketone signals in their 17O‐NMR spectra, the two cyclopropenones 1a, and lb exhibit exceptionally high shielding, indicating a structure closer to a O− formula than to a ketone. For comparison, an enolate and several phenolates have been measured. In order to test the ketonic character, the nucleophilic addition of water was determined by the rate of isotopic O‐exchange between ketone and water: 2 exchanged ca. 20 times slower than acetophenone, whereas la reacted very much more slowly.
The Reaction of 1,3‐Butadiene with Ethyl Diazopyruvate. Syntheses of Salicylates and of Nezukone
Authors: Wenkert Ernest , Greenberg Richard S. , Kim Hong‐Seok 
Published: December 2004

AbstractThe Rh‐catalyzed reaction of 1,3‐butadiene with ethyl 3‐diazopyruvate leads, inter alia, to a dihydro‐oxepinecarboxylate whose oxidation and functinal‐group manipulation produce salicylates. Wittig reactions on the acylcyclopropane accompanying the dihydrooxepine yields acrylates whose pyrolyses afford cycloheptadiene‐carboxylates. Oxidation and functional‐group transformation produces the natural tropone, nezukone.
Benzolactone und Benzocarbocyclen durch Ringerweiterung von Benzocycloalkenonen
Authors: Benkert Erwin , Hesse Manfred 
Published: December 2004

Benzolactones and Benzocarbocycles by Ring Enlargement of Benzocycloalkenone DerivativesThe Michael adducts 5–8 of benzonitrocycloalkenones 1–4 and acrylaldehyde are converted with (CH3)2 Ti(iPrO)2 or NaCNBH3 to secondary and primary alcohols, 9–12 and 13–16, respectively. These alcohols react under basic conditions to form ring‐enlarged benzonitrolactones and benzooxolactones (Scheme 1). The configuration of the bicyclic intermediates in this enlargement step is discussed. The Michael reactions of benzonitrocycloalkenones with methyl vinyl ketone lead to oxoalkyl‐benzonitrocycloalkenones 35‐‐38. These products rearrange in the presence of t‐BuOK to yield benzonitrocycloalkenones 42, 44, and 46, enlarged by two C‐atoms, or tricyclic hydroxy compounds 39, 41, 43, and 45 (Scheme 4).
Substrate and Positional Selectivity of Free Phenylium Ions toward Arenes in the Gas and Liquid Phases
Authors: Angelini Giancarlo , Keheyan Yeghis , Speranza Maurizio 
Published: December 2004

AbstractA nuclear technique, based on the spontaneous decay of tritiated precursors that allows the generation of free carbenium ion of exactly the same nature in different environments, has been exploited in a comparative study of aromatic phenylation by free phenylium ions, both in the gas phase at various pressures and in the liquid phase. The differences between the reactivity pattern of the phenylium ion in the two environments can essentially be reduced to significant ion‐neutral electrostatic interaction in the gas phase and, to the much greater efficiency of collisional stabilization, in the condensed phase, allowing a larger fraction of the excited ionic intermediates, from the highly exothermic attack of phenylium ion on the competing arenes, to survive dissociation and isomerization. The mechanism of the major competitive processes promoted by phenylium‐ion attack on arenes, i.e. phenyldehydrogenation and phenyldephenylation, are discussed, together with the substrate and positional selectivity displayed by the nuclear‐decay‐formed phenylium ion toward the selected arenes. The kinetic and mechanistic features of aromatic phenylation, deduced from the present decay experiments, are compared with those of related phenylation reactions carried out in the dilute gas state and in solution.
High‐Yield Synthesis of 20‐, 24‐, and 28‐Membered Macropentolide, ‐hexolide, and ‐heptolide, Respectively, from (R)‐ or (S)‐3‐hydroxybutanoic acid under Yamaguchi's macrolactonization conditions
Authors: Seebach Dieter , Brändli Urs , Schnurrenberger Peter , Przybylski Michael 
Published: December 2004

AbstractThe macrocyclic pentolide 1, hexolide 2, and heptolide 3 constitute ca. 80% of the oligomers formed in ca. 50% yield from enantiomerically pure 3‐hydroxybutanoic acid under Yamaguchi's macrolactonization conditions. The FAB mass spectra of the MH+, M Na+, and MCs+ are reported (Figs. 2, 3, 5, and 6). No cyclic tetramer is detected. The 1H‐NMR spectra of the cyclic oligomers, of the monomer, and of the polymer (PHB) are very similar (Fig. 4). Directed synthesis of the open‐chain dimer and tetramer of 3‐hydroxybutanoic acid and attempted cyclization do not lead to the isolation of the cyclic tetramer.
Synthese von Dimethyl‐4a,8a‐methanophthalazin‐1,4‐dicarboxylat und Derivaten
Authors: Neidlein Richard , Tadesse Lema 
Published: December 2004

Synthesis of Dimethyl 4a,8a‐Methanophthalazine‐1,4‐dicarboxylate and DerivativesDiels‐Alder reaction with inversed electron demand of 1H‐cyclopropabenzol 1 with dimethyl 1,2,4,5‐tetrazine‐3,6‐dicarboxylate (2) yields dimethyl‐4a,8a‐methanophthalazine‐1,4‐dicarboxylate (3). The reactions of 3 with nucleophiles are also described.
Hydrogénation de sels de flavylium: formation de composés heptacycliques; structure radiocristallographique du [tétrahydro‐10b,10c,16,16a‐diméthyl‐16,16a‐méthylène‐10b,16‐5aH‐di(benzo[1]pyranno)[4,3‐b:3′,4′,‐c;2,3:2′,3′]‐benz[1]oxépinyl‐5a]‐2‐phénol
Authors: Jolibois Henri , Vebrel Joël , Ouahab Lahcene , Boultif Ahmed , Grandjean Daniel 
Published: December 2004

Hydrogenation of Flavylium Salts: Formation of Heptacyclic compounds; X‐Ray Crystal Structure of 2‐[10b,10c,16,16a‐Tetrahydro‐16,16a‐dimethyl‐10b,16‐methylene‐5aH‐di[1]benzopyrano[4,3‐b:3′,4′ ‐c; 2,3:2′,3′][1]benzoxepin‐5a‐yl]phenolThe hydrogenation of flavylium salts 1 either by catalytic reduction or by chemical reduction afforded the unexpected heptacyclic compound 2, the structure of which was determined by X‐ray analysis. The latter was confirmed by 1H‐NMR and mass spectra.
Triaziridine. 9. Mitteilung. Ringöffnungen von Triaziridinen
Authors: Hilpert Hans , Dreiding André S. 
Published: December 2004

Triaziridines. Ring Openings of TriaziridinesEleven triaziridine derivatives were heated at 60° in CDCl3 to obtain information on the tendency towards, resp. the resistance to, ring opening of the N3‐homocycle by thermolysis. Among these triaziridines, there are three which contain, as one of the substituents, a methoxycarbonyl group (ester derivatives 1, 5 and 16), three a methyl group (methyl derivatives 18, 24, and 26), three an H‐atom (14, 27, and 30), and two a negative charge (31 and 32). The other two substituents in each of these four classes of triaziridines are trans‐located i‐Pr groups (1, 18, 27, and 31), cis‐located i‐Pr groups (5, 24, 14, and 32), and a 1,3‐cis‐cyclopentylidene group (16, 26, and 30). As major products these mild thermolyses, we isolated : from the trans‐ester 1 and from the annellated ester derivative 16, the 1‐acyl‐azimines 2 and 17, respectively, from the cis‐ester 5, the 3‐acyl‐triazene 4, from the trans‐methyl derivative 18, the (E)‐diazene 19, and hexamine 21, from the cis‐methyl derivative 24 the 2‐methylazimine 25, both from the trans‐ and cis‐H‐derivatives 27, and 14, respectively, the H‐ triazene 13 and, finally, both from the trans‐and cis‐anion 31 and 32, respectively – after protonation the H‐triazene 13 and – after methylation – the methyl‐triazene 33. The same thermolysis of the annellated methyl and H‐derivatives 26 and 30, respestively, resulted only in decomposition.These results can be uniformly interpreted with a primary opening of the triaziridine ring by rupture of one of the two types of NN bonds lending to azimines or triazenide anions. Some of the azimines were isolable, namely 2, 17, and 25, and one was spectroscopically observable as an intermediate, namely 11 on the way to the triazene 4. The other azimines are plausible intermediates to the isolated products, namely 15 on the way to 13, and 22 on the way to 19 and 21. The triazenide anion 28 is the evident intermediate on the way to 13 or to 33. The annellated azimines are assumed not be formed from 26 and 30, or then to be be decomposed under the conditions of their formation. We conclude that the triaziridine derivatives 1, 16, and 18 underwent thermal ring opening between N(1) and N(2), while the derivatives 5, 14, 24, 27, 31, and 32 were ruptured between N(2) and N(3); no conclusion was possible on the ring opening of the derivatives 26 and 30.The predominant formation of the (Z)‐azimine 2 from the trans‐triaziridine 1, and of the (E)‐isomer 3 – among the two azimines – from the cis‐triaziridine 5 suggests a stereospecificity in the triaziridine ring openings. This would, however, not be expected to be observable in the products from the other triaziridines, since both NN bonds of the azimine 25 and of the anion 28 probably rotate rapidly and since the secondary trans formations of the other primary products are not able to retain configurational information.
The Synthesis and Photoisomerization of 5‐Methyl‐5‐Vinyl‐1,3‐Cyclopentadiene
Authors: Burger Ulrich , Pamingle‐Cristoforetti Eliane , Bringhen Alain O. 
Published: December 2004

AbstractA versatile scheme for the synthesis of geminally disubstituted cyclopentadienes is used to prepare the title compound 4. This remarkably stable vinyl‐cyclopentadiene, distinguished by its Cs symmetry, undergoes exclusively electrocyclic ring closure upon direct π–π* excitation at 254 nm. The epimeric vinyl‐housenes 11 and 12, which, for geometric reasons, are insensitive to the walk rearrangement, are suggested to be the primary photo‐products. One of them, 12, due to its syn‐oriented vinyl group, undergoes spontaneous copy rearrangement to give 2‐methylbicyclo[3.2.1]hepta‐2,6‐diene (13). The other, 11, having an anti‐oriented vinyl group, can only undergo thermal return to the starting material 4. Whereas no leakage to a 1,5‐vinyl migration is discernible for the S1 state of 4, the benzophenone‐sensitized photolysis at 350 nm is shown to be governed by this rearrangement. 1‐Methyl‐5‐vinylcyclopenta‐1,3‐diene (14), the unstable primary product of the sensitized photoreaction, is trapped by 4‐phenyl‐3H‐1,2,4‐triazole‐3,5(4H)‐dione (PTAD).
Ferroelectric Liquid Crystals. Part 2. Chiral phenyl benzoates incorporating a trans‐1,4‐disubstituted cyclohexane ring
Authors: Kelly Stephen M. , Buchecker Richard 
Published: December 2004

AbstractAbout forty novel phenyl benzoates also incorporating a trans‐1,4‐disubstituted cyclohexane ring and a chiral centre have been prepared. The dependence of the liquid‐crystal transition temperatures of this new class of compounds on lateral substituents, diverse central linkages, chain lengths, and position of the chiral centre has been studied systematically. The synthesis and liquid‐crystal transition temperatures of these new compounds are described in detail.
Ferroelectric Liquid Crystals. Part 3. Achiral phenyl benzoates incorporating a trans‐4‐pentylcyclohexyl moiety
Authors: Kelly Stephen M. , Buchecker Richard 
Published: December 2004

AbstractAbout twenty substituted phenyl benzoates incorporating a trans‐4‐pentylcyclohexyl moiety have been synthesised. The synthesis, liquid‐crystal transition temperatures, and enthalpies of fusion are reported. The effect of variations in chainlength and central linkage on the liquid‐crystal transition temperatures is discussed.
[4+2]‐Cycloadditionen von α,β‐ungesättigten Hydrazonen. Teil 2. Pyridin‐2,3‐dicarboximide aus 1,4‐Dihydropyridin‐Derivaten
Authors: Waldner Adrian 
Published: December 2004

[4+2] Cycloaddition of α,β‐Unsaturated Hydrazones to Pyridine‐2,3‐dicarboximides via 1,4‐Dihydropyridine DerivativesThe [4 + 2] cycloaddition of α,β‐unsaturated hydrazones of type 1 (1‐aza‐1,2‐butadienes) with maleimides (e.g. 2b) affords the tetrahydropyridines of type 8. Elimination of dimethylamine to 9 is easily achieved by treatment of 8 with silica gel at elevated temperature. Oxidation of the dihydropyridines 9 leads to highly substituted pyridine‐2,3‐dicarboxylic‐acid dervatives 4.
Dediazoniations of arenediazonium ions. Part 26 Influence of Substituents on the Formation of Benzoic Acids in Reactions of Aryl‐Cation‐Type Intermediates with CO
Authors: Ravenscroft Michael D. , Skrabal Peter , Weiss Bettina , Zollinger Heinrich 
Published: December 2004

AbstractThe N2‐molecule‐aryl‐cation pair formed as the first intermediate in dediazoniations of arenediazonium ions can be trapped with CO in H2O with formation of the corresponding arenecarboxylic acids. This reaction is considered as a model for the reverse of dediazoniation, since CO is isoelectronic with N2. The evaluation of the yields of arenecarboxylic acids formed from substituted benzenediazonium ions using Taft's dual substituent parameter treatment demonstrates that the field reaction constant pF and the resonance reaction constant pR are positive and negative, respectively, as expected for a reaction which corresponds electronically to the addition of N2 to aryl cations.
Synthesis and Structure of Carbonyliron Complexes of Allenecarboxylates and Allenic Lactones
Authors: Trifonov Latchezar S. , Orahovats Alexander S. , Prewo Roland , Heimgratner Heinz 
Published: December 2004

AbstractOn irradiation in the presence of Fe(CO)5, the allenecarboxylates 1 afforded binuclear carbonyliron complexex 6 (Scheme 3), whereas the allenic lactone 7 under similar conditions gave a mixture of one binuclear and two mononuclear carbonyliron complexes (9,8, and 10; Scheme 4). The structure of the complexes has been elucidated by X‐ray crystallography. The structure of the binuclear complex 9 corresponds to that of 6, while 8 has been shown to be a 1,3‐butadiene(tricabonyl)iron complex. The unique structure of the 10 represents a new type of allenic complex. A stepwise formation of the complexes via intermediate allene(tetracarbonyl) iron complexes type 11 and 13 is suggested. Treatment of the binuclear complex 6b with FeCl3 led to the formation of the free ligand and a mixture of mononuclear complexes 13 and 14 (Scheme 5). On heating, the 1,3‐diene complex 8 yielded the free ligand 15, the prouduct of a (1,3) H shift in the allene 7; the complex 10 on the other hand liberates 7 on treatment with ethylenetracarbonitrile (TCNE) (Scheme 6).
Complexation of Cu2+ by Binucleating Macrocycles Containing the N6 Donor Set
Authors: Cruse Richard W. , Kaderli Susan , Spieler Walter , Zuberbühler Andreas D. 
Published: December 2004

AbstractThe hexadentate ligands 1,4,7,12,15,18‐hexaazacyclododecosane ([2]aneN6) and 1,4,7,14,17,20‐hexaazacyclohexacosane ([26]aneN6) both form eight complexes with Cu2+, three of them being binuclear. The corresponding stability constants have been determined potentiometrically, and the electronic absorption spectra have been obtained from spectrophotometric data. Possible interactions of the Cu2+ pairs in the three binuclear complexes have, in addition, been investigated by ESR and and linear ‐sweep voltammetry (LSV). The binuclear complex of [22]aneN6 with one addditional OH group is exceptionally stable, ESR‐silent, and the results of the LSV‐experiments are characteristically different from those of the other binuclear complexes with both ligands. This indicates that [22]aneN6 forms a very stable hydroxo‐bridged binuclear Cu2+ complex Cu2L(OH)3+, whereas in the case of [26]andN6 no bridged Cu2+ pair exists.
Une synthèse générale des tétraazamacrocycles mono‐C‐fonctionnalisés
Authors: Benabdallah Tayeb , Guglielmetti Robert 
Published: December 2004

A General Synthesis for Mono‐C‐Functionalized TetrazamacrocyclesA new synthesis, under usual conditions of concentration, medium, and temperature, of a series of mono‐C‐functionalized tetraazamacrocycles is given. The method may easily be generalized. The new procedure allows the modification of the length of the side‐chain or the size of the cavity by choosing fitted staring materials. The key intermediate has a tosylated linear side‐chain susceptible to be transformed into a large variety of functional groups.