The direct, enantioselective, one-pot, three-component, Cross-Mannich reaction of aldehydes:: The reason for the higher reactivity of aldimine versus aldehyde in proline-mediated Mannich and aldol reactions

被引：42

作者：

Hayashi, Y ^{[1
]}

Urushima, T

Shoji, M

Uchimaru, T

Shiina, I

机构：

[1] Tokyo Univ Sci, Fac Engn, Dept Ind Chem, Shinjuku Ku, Tokyo 1628601, Japan

[2] Natl Inst Adv Ind Sci & Technol, Res Inst Computat Sci, Tsukuba, Ibaraki 3058568, Japan

[3] Tokyo Univ Sci, Fac Sci, Dept Appl Chem, Shinjuku Ku, Tokyo 1628601, Japan

来源：

ADVANCED SYNTHESIS & CATALYSIS | 2005年 / 347卷 / 11-13期

关键词：

asymmetric synthesis; imines; Mannich reaction; organocatalysis; proline;

D O I：

10.1002/adsc.200505190

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

In the proline-mediated Mannich and aldol reactions of propanal as a nucleophile, the aldimine prepared from benzaldehyde and p-anisidine is about 7 times more reactive than the corresponding aldehyde, benzaldehyde, as an electrophile. This higher reactivity of aldimine over aldehyde is attributed to the carboxylic acid of proline protonating the basic nitrogen atom of the aldimine more effectively than the oxygen atom of the aldehyde, an explanation which has been both experimentally and theoretically verified.

引用

页码：1595 / 1604

页数：10

共 118 条

[1] Enantioselective Mannich-type reaction catalyzed by a chiral Bronsted acid [J].

Akiyama, T ;

Itoh, J ;

Yokota, K ;

Fuchibe, K .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2004, 43 (12) :1566-1568

[2]

Akiyama T, 2002, ADV SYNTH CATAL, V344, P338, DOI 10.1002/1615-4169(200206)344:3/4<338::AID-ADSC338>3.0.CO

[3]

2-O

[4] Chemoselective allylation of aldimine with allyltriethylgermane by the combined use of BF3•OEt2 and AcOH [J].

Akiyama, T ;

Iwai, J ;

Onuma, Y ;

Kagoshima, H .

CHEMICAL COMMUNICATIONS, 1999, (21) :2191-2192

[5] Chemoselective activation of aldimine in preference to aldehyde by the combination of BF3•OEt2 and water:: Novel catalyst for the Mannich-type reaction [J].

Akiyama, T ;

Takaya, J ;

Kagoshima, H .

CHEMISTRY LETTERS, 1999, (09) :947-948

[6] HBF4 catalyzed Mannich-type reaction in aqueous media [J].

Akiyama, T ;

Takaya, J ;

Kagoshima, H .

SYNLETT, 1999, (07) :1045-1048

[7]

Akiyama T., 2004, ANGEW CHEM, V116, P1592, DOI DOI 10.1002/ANGE.200353240

[8] Theory of asymmetric organocatalysis of aldol and related reactions: Rationalizations and predictions [J].

Allemann, C ;

Gordillo, R ;

Clemente, FR ;

Cheong, PHY ;

Houk, KN .

ACCOUNTS OF CHEMICAL RESEARCH, 2004, 37 (08) :558-569

[9] Diastereoselective addition of chlorotitanium enolate of N-acyl thiazolidinethione to O-methyl oximes:: A novel, stereoselective synthesis of α,β-disubstituted β-amino carbonyl compounds via chiral auxiliary mediated azetine formation [J].

Ambhaikar, NB ;

Snyder, JP ;

Liotta, DC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (13) :3690-3691

[10]

Asao N, 2001, ANGEW CHEM INT EDIT, V40, P3206, DOI 10.1002/1521-3773(20010903)40:17<3206::AID-ANIE3206>3.0.CO

← 1 2 3 4 5 6 7 8 9 10 →