Synthetic studies on macrolactin A by using a (diene)Fe(CO)3 complex

The stereoselective synthesis of the two segments 3 and 4 of macrolactin A 1 is described. Macrolactin A is a 24-membered polyene macrolide antibiotic, which is of interest due to a strong activity against B16-F10 murine tumor cell and HIV-1 virus. The key step of the synthesis is the 1,2-migration reaction of a (diene)Fe(CO)₃ complex with a introduction of the thiol group to construct the unstable (E,Z)-conjugated dienic moiety (C8-C11).     

A new class of aromatic polyetheraroylhydrazides. I. Synthesis and chemical–physical characterization

A series of new aromatic polyetheraroylhydrazides incorporating 4-oxybenzoyl units has been synthesized, whose general formula was [CONHNHCO? O? O–(CH₂)_x? O? phenyl O-CONHNHCOO]_n with x values in the range of 2 to 12. The increasing number of methylene units in the backbone gave rise to polymers which melted before the hydrazidic linkage underwent thermal cyclation to oxadiazole. Moreover, many polymers showed multiple endotherms on melting. X-ray diffraction studies confirmed a crystalline organization of polyhydrazides for methylene units above 4. © 1993 John Wiley & Sons, Inc.     

Solid Phase Synthesis of 4H-Pyrimido[2,1-b] Benzothiazol-4-ones from Resin-Bound Cyclic Malonic Ester

The solid phase synthesis of 4H-pyrimido[2,1-6] benzothizaol-4-ones has been reported.     

An improved cyclization protocol for the synthesis of diazabicyclo[4.3.0]alkanes

We have recently described the synthesis of diazabicyclo[4.X.0]alkanes and their use as ligands for the prostate specific membrane antigene (PSMA). The key step of our synthetic route toward these diazabicycloalkanes is an oxidative cleavage of a bicyclic diol moiety followed by the attack of a nitrogen nucleophile to the resulting intermediate bisaldehyde. We herein describe the mechanism of this ring closure and its stereochemical consequences. In addition, we report a convenient method for trapping intermediate bisaldehydes by Wittig reagents. This trapping allows the synthesis of 3,5-disubstituted proline derivatives, which are shown to be versatile precursors for functionalized diazabicycloalkane dipeptide mimetics.     

INTRAPARTICLE DIFFUSION EFFECTS IN FISCHER-TROPSCH SYNTHESIS Ⅰ. MODELING OF DIFFUSION AND REACTION

IntroductionCatal}ticrcactionsaffcctcdb}'diffosionaIlimitationincatal}'stporcshavcbccnextensive1}dcaltx`ithinlit.rat.rcll~5I.Scvcraltcchniqucsonthcspccialcase0fFischcr-Tropschs}'nthcsis(FTS)t\crcapplicdtocxplorcthebchaviorofthiscatal}ticrcactionundercxpcrimcntalandopcrationaIconditionsI3~5l.It`"ouldbeofvaluctoindicatchcrcthatthcseinvcstigationsx"ercmainl}'bascdonthesimplcstkineticsofthcfirstordcrinH2proposedbyAndersonl6]attheearIystages.However-thesetboents,striCtlyspeaking,areinvalidfor…     

A practical approach to the fused β-carboline system. Asymmetric synthesis of indolo[2,3-a]indolizidinones via a diastereoselective intramolecular α-amidoalkylation reaction

Fused β-carboline systems, as indolo[2,3-a]indolizidinones, indolo[2,3-a]quinolizidinones, their 2-oxa analogues, and benzo[a]indolo[2,3-a]indolizidinones are prepared efficiently via an RLi addition-N-acyliminium ion cyclisation sequence on readily available imides. In an enantioselective variant of these α-amidoalkylation reactions, the addition of MeLi to a chiral non-racemic imide derived from tryptophan yielded an oxo amide, which was cyclised diastereoselectively upon treatment with BF₃·OEt₂, to afford 5,11b-trans-indoloindolizidinone in moderate yield and high ee (99%).     

Synthesis, properties, and structure of dimethylgold(III) complexes [(CH3)2AuI]2 and (CH3)2AuS2CN(C2H5)2

Volatile diethyldithiocarbamate of dimethylgold(III) was prepared by the interaction of dimethylgold(III) iodide with sodium diethyldithiocarbamate. The complex is examined by the elemental analysis, DTA, IR and electronic spectroscopy. The starting dimeric complex [(CH₃)₂AuI]₂ and a novel monomeric volatile gold(III) complex (CH₃)₂AuS₂CN(C₂H₅)₂ with the AuC₂S₂ coordination core were investigated by single crystal X-ray diffraction for the first time.     

A concise synthesis of (2S,4R)- and (2S,4S)-4-methylglutamic acid

A concise, multi-gram scale method for producing the bioactive and enantiomerically pure epimers, (2S,4R)- and (2S,4S)-glutamic acids, in a single synthetic scheme is described.     

N-Nosyl-α-amino acids in solution phase peptide synthesis

A highly efficient and practical synthesis of peptides in solution phase has been developed. The procedure is based on the use of p-nitrobenzenesulfonyl (nosyl) group for the protection of the amino function of α-amino acids. Every step of the procedure, protection of the amino function by the nosyl group, formation of the peptide bond, and removal of the sulfonamide group, is characterized by high yields and excellent purity of the final products. The described strategy allows the preparation of short peptide sequences keeping the chiral integrity of amino acid precursors. Compatibility of nosyl group with the side-chain protecting groups used in Fmoc-based strategy is demonstrated. The method here presented is an alternative strategy that could provide advantages for future peptide synthesis.     

19-Electron arenecyclopentadienyl complexes of ruthenium

A series of are necyc lope ntadienyl complexes,i. e., [Ru(⁵-c₅R₅)(⁶- are ne)]⁺ (1, R= H, arene = C₆H₆; 2, R = Me, arme = C₆H₆; 3, R = H, arctic = C₆H₃Me₃; 4, R = Me, arene = C₆H₃Me₃; 5, R = H, arene = C₆Me₆; 6, R = Me, arene = C₆Me₆) was studied by cyclic voltammetry. These compounds are capable of both oxidation and reduction. The reduction potential values depend on the number of methyl groups in the complex. Reduction of benzene complexes I and 2 by sodium amalgam in THF leads to the formation of decomplexation products, the addition of hydrogen to benzene, and dimerization of the benzene ligands. Both chemical and electrochemical reductions of mesitylene complexes3 and4 result in dimeric products [(⁵-C₅R₅)Ru(-⁵;⁵-Me₃H₃C₆H₃Me₃)Ru(⁵-C₅R₅)] (14, R = H; 15, R = Me). The action of sodium amalgam on compound5 gives products of hydrogen addition to both hexamethylbenzene (17) and cyclopentadienyl (18) ligands along with the major product, the dimer [⁵-C₅H₅)Ru(-⁵; ⁵-Me₆C₆C₆Me₆)Ru(⁵-C₅H₅)] (16). In contrast to5, its permcthylated analog 6 is only capable of adding hydrogen to the hexamethylbenzene ligand.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1691–1697, July, 1996.