Construction of Contiguous Tetrasubstituted Chiral Carbon Stereocenters via Direct Catalytic Asymmetric Aldol Reaction of α-Isothlocyanato Esters with Ketones

被引：117

作者：

Yoshino, Tatsuhiko ^{[1
]}

Morimoto, Hiroyuki ^{[1
]}

Lu, Gang ^{[1
]}

Matsunaga, Shigeki ^{[1
]}

Shibasaki, Masakatsu ^{[1
]}

机构：

[1] Univ Tokyo, Grad Sch Pharmaceut Sci, Bunkyo Ku, Tokyo 1130033, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 47期

关键词：

ENANTIOSELECTIVE SYNTHESIS; AMINO-ACIDS; TERTIARY ALCOHOLS; ALDEHYDES; CONDENSATION; DERIVATIVES; KETIMINES; ADDITIONS;

D O I：

10.1021/ja908571w

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Construction of contiguous tetrasubstituted chiral carbon stereocenters via direct catalytic asymmetric aldol. reaction of a-substituted a-isothiocyanato esters with unactivated simple ketones is described. A Bu2Mg/Schiff base catalyst promoted the aldol addition/cyclization sequence at room temperature, giving protected alpha-amino-beta-hydroxy esters with contiguous tetrasubstituted chiral carbon stereocenters in 99 to 68% yield, 98:2 to 74:26 dr, and 98 to 82% ee.

引用

页码：17082 / +

页数：3

共 31 条

[1] Catalytic Enantioselective Aldol Additions to Ketones [J].

Adachi, Shinya ;

Harada, Toshiro .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2009, 2009 (22) :3661-3671

[2] Direct catalytic enantioselective mannich reactions:: Synthesis of protected anti-α,β-diamino acids [J].

Cutting, Gary A. ;

Stainforth, Nikki E. ;

John, Matthew P. ;

Kociok-Koehn, Gabriele ;

Willis, Michael C. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (35) :10632-+

[3] Lewis base catalyzed, enantioselective aldol addition of methyl trichlorosilyl ketene acetal to ketones [J].

Denmark, SE ;

Fan, Y ;

Eastgate, MD .

JOURNAL OF ORGANIC CHEMISTRY, 2005, 70 (13) :5235-5248

[4] Catalytic, enantioselective aldol additions to ketones [J].

Denmark, SE ;

Fan, Y .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (16) :4233-4235

[5] Highly diastereo- and enantioselective copper-catalyzed domino reduction/aldol reaction of ketones with methyl acrylate [J].

Deschamp, J ;

Chuzel, O ;

Hannedouche, J ;

Riant, O .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2006, 45 (08) :1292-1297

[6] SYNTHESIS OF THE CYCLIC HEXAPEPTIDE ECHINOCANDIN-D - NEW APPROACHES TO THE ASYMMETRIC-SYNTHESIS OF BETA-HYDROXY ALPHA-AMINO-ACIDS [J].

EVANS, DA ;

WEBER, AE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (23) :7151-7157

[7] RATE EQUILIBRIUM CORRELATIONS FOR THE ALDOL CONDENSATION - AN ANALYSIS IN TERMS OF MARCUS THEORY [J].

GUTHRIE, JP .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (19) :7249-7255

[8] THE ALDOL CONDENSATION OF ACETONE WITH ACETOPHENONE [J].

GUTHRIE, JP ;

WANG, XP .

CANADIAN JOURNAL OF CHEMISTRY-REVUE CANADIENNE DE CHIMIE, 1992, 70 (04) :1055-1068

[9] Recent progress in the catalytic synthesis of tertiary alcohols from ketones with organometallic reagents [J].

Hatano, Manabu ;

Ishihara, Kazuaki .

SYNTHESIS-STUTTGART, 2008, 11 (11) :1647-1675

[10] Sodium phenoxide-phosphine oxides as extremely active lewis base catalysts for the mukaiyama aldol reaction with ketones [J].

Hatano, Manabu ;

Takagi, Ed ;

Ishihara, Kazuaki .

ORGANIC LETTERS, 2007, 9 (22) :4527-4530

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