Unique reaction behavior of organozincs toward pi-allylpalladium complexes: Palladium catalyzed synthesis of unsymmetrical ketones and umpolung of pi-allylpalladium

被引:5
作者
Tamaru, Y
机构
[1] Nagasaki Univ, Nagasaki
关键词
functionalized organozincs; carbonylation; pi-allylpalladium; umpolung; allylzincs;
D O I
10.5059/yukigoseikyokaishi.53.1102
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Alkylorganozinc reagents, non-functionalized and functionalized with electrophilic functional groups, e.g., ester, ketone, nitrile, etc., display unique reactivity toward pi-allylpalladium complexes :They do not undergo usual coupling reaction, providing allylalkanes, instead, they form rather stable (reductive elimination resistant) alkylallyipalladium complexes, which either undergo a reductive carbonylative coupling reaction to provide alkyl allyl ketones under carbon monoxide (1 atm; unsymmetrical ketone synthesis via palladium catalyzed three-component coupling reaction of allylic benzoates, carbon monoxide, and alkylorganozincs) or react further with another mole of organozinc reagents to furnish an equilibrium mixture with dialkylpalladium and allylzinc species (umpolung of pi-allylpalladium via transmetailation with organozincs). Stereo-defined allylzincs, generated by this umpolung technique with inversion of configuration at the allylic center of allylic benozoates, react with aldehydes with high regio- and stereoselectivities, Mechanistic details of these unique reactions are discussed.
引用
收藏
页码:1102 / 1113
页数:12
相关论文
共 75 条
[61]   METAL PROMOTED .9. - CONTROLLED AND CATALYTIC ACYLPALLADATION - A NOVEL ROUTE TO CYCLOPENTENONE AND CYCLOHEXENONE DERIVATIVES [J].
TOUR, JM ;
NEGISHI, EI .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1985, 107 (26) :8289-8291
[62]   TRIS(TRIMETHYLSILYL)ALUMINUM AND TRANSITION-METAL CATALYSTS - SILYLATION OF ALLYL ACETATES [J].
TROST, BM ;
YOSHIDA, J ;
LAUTENS, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (13) :4494-4496
[63]   NEW RULES OF SELECTIVITY - ALLYLIC ALKYLATIONS CATALYZED BY PALLADIUM [J].
TROST, BM .
ACCOUNTS OF CHEMICAL RESEARCH, 1980, 13 (11) :385-393
[64]   INVERSION OF THE ELECTRONIC REACTIVITY OF ALLYL ACETATES USING AN ALUMINUM TIN REAGENT [J].
TROST, BM ;
HERNDON, JW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1984, 106 (22) :6835-6837
[65]   CATALYTIC REACTIONS VIA PI-ALLYLPALLADIUM COMPLEXES [J].
TSUJI, J .
PURE AND APPLIED CHEMISTRY, 1982, 54 (01) :197-206
[66]   REMOTE CARBONYLATION - THE SYNTHESIS OF DELTA-LACTONES FROM SATURATED ALCOHOLS AND CARBON-MONOXIDE [J].
TSUNOI, S ;
RYU, I ;
SONODA, N .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (12) :5473-5474
[67]  
VANDERBAAN JL, 1995, SYNLETT, V1
[68]   MIGRATION VERSUS INSERTION IN SQUARE-PLANAR PLATINUM AND PALLADIUM COMPLEXES [J].
VANLEEUWEN, PWNM ;
ROOBEEK, CF ;
VANDERHEIJDEN, H .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (26) :12117-12118
[69]   INSERTION OF CARBON-MONOXIDE INTO NICKEL-ALKYL BONDS OF MONOALKYLNICKEL(II) AND DIALKYLNICKEL(II) COMPLEXES, NIR(Y)L2 AND NIR2L2 - PREPARATION OF NI(COR)(Y)L2 FROM NIR(Y)L2 AND SELECTIVE FORMATION OF KETONE, DIKETONE, AND ALDEHYDE FROM NIR2L2 [J].
YAMAMOTO, T ;
KOHARA, T ;
YAMAMOTO, A .
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1981, 54 (07) :2161-2168
[70]   SELECTIVE REACTIONS USING ALLYLIC METALS [J].
YAMAMOTO, Y ;
ASAO, N .
CHEMICAL REVIEWS, 1993, 93 (06) :2207-2293