Reaction of the lithio-derivative of methoxyallene with hydrazones.: Part 1:: Synthesis and transformation of α-allenyl hydrazines

被引：30

作者：

Breuil-Desvergnes, V ^{[1
]}

Goré, J ^{[1
]}

机构：

[1] Univ Lyon 1, CNRS, Lab Chim Organ 1, F-69622 Villeurbanne, France

来源：

TETRAHEDRON | 2001年 / 57卷 / 10期

关键词：

organolithium; allenes; asymmetric synthesis; pyrrolines; pyrroles;

D O I：

10.1016/S0040-4020(01)00030-8

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The lithio-derivative of methoxyallene reacts with aldehyde hydrazones leading to expected alpha -allenyl hydrazines when ether is the solvent of the reaction. The yields are good as well as the diastereoselectivity observed in the case of SAMP-hydrazones. These hydrazines are cleanly transformed to N-dialkylamino-3-methoxy-3-pyrrolines when they are reacted with n-BuLi in THF. These compounds are sometimes accompanied by the isomeric 4-methyl azetidines. The N-diallcylamino-3-methoxy-3-pyrrolines are transformed to 3-methoxy-3-pyrrolines by hydrogenolysis of the nitrogen-nitrogen bond, to 3-alkoxy-pyrroles by treatment with a peracid and to 3-amino-pyrroles by acidic migration of the dialkylamino group. In the case of SAMP-hydrazines, the obtained 3-methoxy-3-pyrrolines have a high enantiomeric purity. Lastly, attempts to prepare alpha -hydrazino-esters (and subsequently alpha -amino-esters) by ozonolysis of the allenyl moiety failed due to the formation of a methyl glyoxylate. (C) 2001 Elsevier Science Ltd. All rights reserved.

引用

页码：1939 / 1950

页数：12

共 61 条

[1]

ALEXAKIS A, 1991, SYNLETT, P625

[2]

ALEXAKIS A, 1995, SYNTHESIS-STUTTGART, P1038

[3]

Amombo MO, 1999, SYNLETT, P1871

[4] Stereochemistry .87. Synthesis of chiral non-racemic 2-arylpyrrolines by a [3+2] cycloaddition route [J].

Balasubramanian, T ;

Hassner, A .

TETRAHEDRON LETTERS, 1996, 37 (32) :5755-5758

[5] A facile synthesis of 3-alkoxy and 3-amino pyrroles [J].

Breuil-Desvergnes, V ;

Compain, P ;

Vatèle, JM ;

Goré, J .

TETRAHEDRON LETTERS, 1999, 40 (50) :8789-8792

[6] Reaction of the lithio-derivative of methoxy allene with SAMP-hydrazones:: Access to enantiopure 3-pyrrolines [J].

Breuil-Desvergnes, V ;

Compain, P ;

Vatèle, JM ;

Goré, J .

TETRAHEDRON LETTERS, 1999, 40 (27) :5009-5012

[7] Reaction of the lithio-derivative of methoxyallene with hydrazones.: Part 2:: Formation of 3-pyrrolines and azetidines;: synthetic and mechanistic aspects [J].

Breuil-Desvergnes, V ;

Goré, J .

TETRAHEDRON, 2001, 57 (10) :1951-1960

[8] ENANTIOSELECTIVE HYDROGENATION OF THE C=N GROUP - A CATALYTIC ASYMMETRIC REDUCTIVE AMINATION PROCEDURE [J].

BURK, MJ ;

FEASTER, JE .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (15) :6266-6267

[9] THE PROTECTING DIRECTING ROLE OF THE TRITYL GROUP IN SYNTHESES OF PYRROLE DERIVATIVES - EFFICIENT PREPARATIONS OF 1-H-PYRROLE-3-CARBOXYLIC ACID AND 3-ACYL-1-TRITYLPYRROLES, 3-AMINO-1-TRITYLPYRROLES, AND 3-BROMO-1-TRITYLPYRROLES [J].

CHADWICK, DJ ;

HODGSON, ST .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1983, (01) :93-102

[10] ALLENES AND ACETYLENES .18. SYNTHESIS OF 3-PYRROLINES BY SILVER(I)-CATALYZED CYCLIZATION OF ALLENIC AMINES [J].

CLAESSON, A ;

SAHLBERG, C ;

LUTHMAN, K .

ACTA CHEMICA SCANDINAVICA SERIES B-ORGANIC CHEMISTRY AND BIOCHEMISTRY, 1979, 33 (04) :309-310

← 1 2 3 4 5 6 7 →