Generation of phosphorus-centered radicals via homolytic substitution at sulfur

被引:79
作者
Carta, Paola [1 ]
Puljic, Nicolas [1 ]
Robert, Carine [1 ]
Dhimane, Anne-Lise [1 ]
Fensterbank, Louis [1 ]
Lacote, Emmanuel [1 ]
Malacria, Max [1 ]
机构
[1] Univ Paris 06, Chim Organ Lab, UMR 7611, CNRS,Inst Chim Mol FR 2769, F-75005 Paris, France
关键词
D O I
10.1021/ol0631096
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A novel radical domino process relying on the homolytic cleavage of P-S bonds allows the preparation of phosphorus-containing molecules through addition of P-centered radicals onto olefins. The key step of this reaction is a homolytic substitution on a sulfur atom. The scope of the reaction is broad. Diaminophosphonyl radicals whose reactivity was unknown react smoothly with olefins. Use of tin hydride can be avoided. A radical thiophosphinoylation of triple bonds has been uncovered.
引用
收藏
页码:1061 / 1063
页数:3
相关论文
共 39 条
[1]   Dimethyl phosphite mediated hydrogen atom abstraction:: A tin-free procedure for the preparation of cyclopentane derivatives [J].
Beaufils, F ;
Dénès, F ;
Renaud, P .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2005, 44 (33) :5273-5275
[2]   CENTENARY LECTURE - THE PURSUIT OF SELECTIVITY IN RADICAL REACTIONS [J].
BECKWITH, ALJ .
CHEMICAL SOCIETY REVIEWS, 1993, 22 (03) :143-151
[3]   Generation and cyclization of unsaturated carbamoyl radicals derived from S-4-pentynyl carbamothioates under tin-free conditions [J].
Benati, L ;
Bencivenni, G ;
Leardini, R ;
Minozzi, M ;
Nanni, D ;
Scialpi, R ;
Spagnolo, P ;
Zanardi, G .
JOURNAL OF ORGANIC CHEMISTRY, 2006, 71 (08) :3192-3197
[4]   Generation and intramolecular reactivity of acyl radicals from alkynylthiol esters under reducing tin-free conditions [J].
Benati, L ;
Calestani, G ;
Leardini, R ;
Minozzi, M ;
Nanni, D ;
Spagnolo, P ;
Strazzari, S .
ORGANIC LETTERS, 2003, 5 (08) :1313-1316
[5]   Intramolecular cyclization of acyl radicals onto the azido group: A new radical approach to cyclized lactams [J].
Benati, L ;
Leardini, R ;
Minozzi, M ;
Nanni, D ;
Spagnolo, P ;
Strazzari, S ;
Zanardi, G .
ORGANIC LETTERS, 2002, 4 (18) :3079-3081
[6]  
Bentrude W. G., 1990, The Chemistry of Organophosphorus Compounds, V1, P531, DOI 10.1002/9780470034439m
[7]   PHOSPHORANYL RADICALS - THEIR STRUCTURE, FORMATION, AND REACTIONS [J].
BENTRUDE, WG .
ACCOUNTS OF CHEMICAL RESEARCH, 1982, 15 (04) :117-125
[8]   5-endo-trig radical cyclizations of bromomethyldimethylsilyl diisopropylpropargylic ethers.: A highly diastereoselective access to functionalized cyclopentanes [J].
Bogen, S ;
Gulea, M ;
Fensterbank, L ;
Malacria, M .
JOURNAL OF ORGANIC CHEMISTRY, 1999, 64 (13) :4920-4925
[9]  
CHIESSER CH, 2006, CHEM COMMUN, P4055
[10]   Free radical chemistry of nucleosides and nucleotides.: Ring opening of C4′-radicals [J].
Crich, D ;
Yao, QW .
TETRAHEDRON, 1998, 54 (3-4) :305-318