Enantioselective Decarboxylative Alkylation Reactions: Catalyst Development, Substrate Scope, and Mechanistic Studies

被引：162

作者：

Behenna, Douglas C. ^{[1
]}

Mohr, Justin T. ^{[1
]}

Sherden, Nathaniel H. ^{[1
]}

Marinescu, Smaranda C. ^{[1
]}

Harned, Andrew M. ^{[1
]}

Tani, Kousuke ^{[1
]}

Seto, Masaki ^{[1
]}

Ma, Sandy ^{[1
]}

Novak, Zoltan ^{[1
]}

Krout, Michael R. ^{[1
]}

McFadden, Ryan M. ^{[1
]}

Roizen, Jennifer L. ^{[1
]}

Enquist, John A., Jr. ^{[1
]}

White, David E. ^{[1
]}

Levine, Samantha R. ^{[1
]}

Petrova, Krastina V. ^{[1
]}

Iwashita, Akihiko ^{[1
]}

Virgil, Scott C. ^{[1
]}

Stoltz, Brian M. ^{[1
]}

机构：

[1] CALTECH, Div Chem & Chem Engn, Warren & Katharine Schlinger Lab Chem & Chem Engn, Pasadena, CA 91125 USA

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2011年 / 17卷 / 50期

关键词：

alkylation; allylic compounds; asymmetric catalysis; enolates; reaction mechanisms; synthetic methods; ASYMMETRIC ALLYLIC ALKYLATION; PI-ALLYLPALLADIUM COMPLEXES; QUATERNARY CARBON CENTERS; FORMING REDUCTIVE ELIMINATION; TRANSITION-METAL CATALYSIS; FORMAL TOTAL-SYNTHESIS; SILYL KETENE IMINES; NUCLEOPHILIC-ATTACK; ALLYLATION REACTION; BOND FORMATION;

D O I：

10.1002/chem.201003383

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

alpha-Quaternary ketones are accessed through novel enantioselective alkylations of allyl and propargyl electrophiles by unstabilized prochiral enolate nucleophiles in the presence of palladium complexes with various phosphinooxazoline (PHOX) ligands. Excellent yields and high enantiomeric excesses are obtained from three classes of enolate precursor: enol carbonates, enol silanes, and racemic beta-ketoesters. Each of these substrate classes functions with nearly identical efficiency in terms of yield and enantioselectivity. Catalyst discovery and development, the optimization of reaction conditions, the exploration of reaction scope, and applications in target-directed synthesis are reported. Experimental observations suggest that these alkylation reactions occur through an unusual inner-sphere mechanism involving binding of the prochiral enolate nucleophile directly to the palladium center.

引用

页码：14199 / 14223

页数：25

共 294 条

[81] The total synthesis of (-)-cyanthiwigin F by means of double catalytic enantioselective alkylation [J].

Enquist, John A., Jr. ;

Stoltz, Brian M. .

NATURE, 2008, 453 (7199) :1228-1231

[82]

Evans D.A., 1999, COMPREHENSIVE ASSYME, V3, P1177

[83] Enantioselective rare-earth catalyzed quinone Diels-Alder reactions [J].

Evans, DA ;

Wu, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (34) :10162-10163

[84] Conservation of absolute configuration in the acyclic rhodium-catalyzed allylic alkylation reaction:: Evidence for an enyl (σ+π) organorhodium intermediate [J].

Evans, PA ;

Nelson, JD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (22) :5581-5582

[85] Asymmetric nickel-catalyzed negishi cross-couplings of secondary α-bromo amides with organozinc reagents [J].

Fischer, C ;

Fu, GC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (13) :4594-4595

[86] Nucleophilic chiral amines as catalysts in asymmetric synthesis [J].

France, S ;

Guerin, DJ ;

Miller, SJ ;

Lectka, T .

CHEMICAL REVIEWS, 2003, 103 (08) :2985-3012

[87] ASYMMETRIC CREATION OF QUATERNARY CARBON CENTERS [J].

FUJI, K .

CHEMICAL REVIEWS, 1993, 93 (06) :2037-2066

[88] The utility of the classical and oxidative Heck reactions in natural product synthesis: Studies directed toward the total synthesis of dragmacidin F [J].

Garg, Neil K. ;

Caspi, Daniel D. ;

Stoltz, Brian M. .

SYNLETT, 2006, (18) :3081-3087

[89] A unified synthetic approach to the pyrazinone dragmacidins [J].

Garg, Neil K. ;

Stoltz, Brian M. .

CHEMICAL COMMUNICATIONS, 2006, (36) :3769-3779

[90] Development of an enantiodivergent strategy for the total synthesis of (+)- and (-)-dragmacidin F from a single enantiomer of quinic acid [J].

Garg, NK ;

Caspi, DD ;

Stoltz, BM .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (16) :5970-5978

← 4 5 6 7 8 9 10 11 12 13 →