Stereoselective Addition to N-Activated Pyridines James A. Bull,‡ James J. Mousseau, Guillaume Pelletier,† and Andre ́ B. Charette*,† †Department of Chemistry, Universite ́ de Montreál, P.O. Box 6128, Station Downtown, Montreál, Queb́ec, Canada H3C 3J7 ‡Department of Chemistry, Imperial College London, South Kensington, London SW7 2AZ, U.K. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA

Synthesis of Pyridine and Dihydropyridine Derivatives by Regio- and Stereoselective Addition to N-Activated Pyridines

Aldehyde N,N-Dialkylhydrazones as Neutral Acyl Anion Equivalents: Umpolung of the Imine Reactivity

for Organic Synthesis Valentine G. Nenajdenko,*,†,§ Vasiliy M. Muzalevskiy,† and Aleksey V. Shastin†,‡ †Department of Chemistry, Moscow State University, Leninskie Gory, Moscow 119992, Russia ‡The Institute of Problems of Chemical Physics of the Russian Academy of Sciences (IPCP RAS), Chernogolovka, Moscow Region 142432, Russia A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences (INEOS RAS), 119991, GSP-1, Moscow, V-334, Vavilova St. 28, Russia

Polyfluorinated ethanes as versatile fluorinated C2-building blocks for organic synthesis.

Thiazolyl-phosphine hydrochloride salts: effective auxiliary ligands for ruthenium-catalyzed nitrile hydration reactions and related amide bond forming processes in water

4-Selenophosphoryl-1,2-disubstituted imidazoles have been obtained by thermal decomposition of methyl 5-(diamidoselenophosphoryl)imidazolium chlorides. The position of selenophosphoryl group in the imidazole ring was proved by 1H, 13C NMR spectroscopy, and X-ray analysis. Previously unknown diamido- and dichloro(imidazol-4-yl)- phosphonites were synthesized, and differences in their reactivity compared to analogous 5-phosphorylated imidazoles are shown. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:103–118, 2010; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20584

4‐Phosphorylated 1,2‐disubstituted imidazoles

1,2-Disubstituted imidazoles react with phosphorus(III) halides in pyridine regioselectively at position 5. The reaction proceeds the more readily, the higher the electron-donating ability of the 2-substituent in the starting imidazole. Hitherto unknown dihalo(imidazol-5-yl)phosphines have been obtained, and their properties have been studied. Also synthetic methods for the preparation of various monohalo(organyl)(imidazolyl)phosphines have been developed. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:289–308, 2009; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.20550

5-phosphorylated 1,2-disubstituted imidazoles†

2-(3-Methyl-1,3-diazabuten-1-yl)-3-ethoxycarbonylthiophenes are phosphorylated with phosphorus(III) halides in basic media at position 5 of the thiophene ring. Up to three heteroaromatic substituents can be introduced one by one at the same phosphorus atom. On this basis, mono-, bis-, and trishetaryl substituted P(III) and P(V) derivatives have been obtained. Phosphorylated 2-(N,N-dimethylformamidino)-3-ethoxycarbonylthiophenes provide a synthetic access to phosphorylated thienopyrimidines. © 2001 John Wiley & Sons, Inc. Heteroatom Chem 12:641–651, 2001

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Phosphorylation of 2‐(3‐methyl‐1,3‐diazabuten‐1‐yl)‐3‐ethoxycarbonylthiophenes with phosphorus(III) halides

Phosphorylation of 4- and 1-substituted 1,2,4-triazoles with PCl3, PhPCl2, Ph2PCl, and (Et2N)2 PCl was carried out. A novel phosphorus-containing condensed heterocyclic system (18, 23) was constructed by the reactions of 2-(1H-1,2,4-triazol-1-yl)-1-(4-chlorophenylcarboxamido)-5-trifluoromethylbenzene with PBr3 and PhPBr2. Treatment of the bromophosphonite 18 with an excess of morpholine in the presence of sulfur resulted in a diazaphosphinine ring opening and provided functionalized 1H-1,2,4-triazol-5-ylphosphonic acid derivatives 21 and 22. © 2002 Wiley Periodicals, Inc. Heteroatom Chem 13:146–152, 2002; Published online in Wiley Interscience (www.interscience.wiley.com). DOI 10.1002/hc.10010

C-phosphorylation of 1,2,4-triazoles with phosphorus(III) halides. Synthesis of 4,5-dihydrobenzo[e][1,2,4]triazolo[5,1-c][1,4,2]diazaphosphinine derivatives

A number of 4,5-dihydrobenzo[e]imidazo[2,1-c][1,4,2]diazaphosphinine derivatives were prepared by the direct phosphorylation of 1-(4-Chlorophenylcarboxamido)-2-(1H-1-imidazolyl)-5-trifluoromethylbenzene in basic medium with phosphorus(III) bromide and dibromophenylphosphine. The tricyclic compounds 6a,6b, and 9 having a trivalent phosphorus atom undergo the diazaphosphinine ring opening upon treatment with secondary amines in the presence of sulfur. © 2002 John Wiley & Sons, Inc. Heteroatom Chem 13:84–92, 2002; DOI 10.1002/hc.10000

Alexandr M. Pinchuk

Papers

5-phosphorylated 1,2-disubstituted imidazoles†

Phosphorylation of 2‐(3‐methyl‐1,3‐diazabuten‐1‐yl)‐3‐ethoxycarbonylthiophenes with phosphorus(III) halides

C-phosphorylation of 1,2,4-triazoles with phosphorus(III) halides. Synthesis of 4,5-dihydrobenzo[e][1,2,4]triazolo[5,1-c][1,4,2]diazaphosphinine derivatives

Synthesis and properties of 4,5‐dihydrobenzo[e]imidazo[2,1‐c][1,4,2]diazaphosphinine derivatives

Addition of some aminoheterocycles to N-benzyl-3-cyanopyridinium chloride