Sequential Copper-Catalyzed Rearrangement-Allylic Substitution of Bicyclic Hydrazines with Grignard Reagents

被引：27

作者：

Crotti, Stefano ^{[1
]}

Bertolini, Ferruccio ^{[1
]}

Macchia, Franco ^{[1
]}

Pineschi, Mauro ^{[1
]}

机构：

[1] Univ Pisa, Dipartimento Sci Farmaceut, I-56126 Pisa, Italy

来源：

ADVANCED SYNTHESIS & CATALYSIS | 2009年 / 351卷 / 06期

关键词：

allylic alkylation; copper; Grignard reagents; rearrangement; sequential reactions; STEREOSELECTIVE-SYNTHESIS; ENANTIOSELECTIVE DESYMMETRIZATION; RING; ISOMERIZATION; DIAZABICYCLES; REACTIVITY; INHIBITOR;

D O I：

10.1002/adsc.200900037

中图分类号：

O69 [应用化学];

学科分类号：

081704 ;

摘要：

The problem of the synthesis of trans-1,4-disubstituted hydrazino- and aminocyclopentenes has been resolved by a sequential copper-catalyzed rearrangement-allylic alkylation of 2,3-diazabicyclo-[2.2.1]heptenes. The cis-fused 5,5-membered allylic carbazate which is formed in situ by a novel copper(H) triflate [Cu(OTf)(2)]/(+/-)-BINAP-catalyzed rearrangement, can be alkylated with a broad spectrum of Grignard reagents with a predominant S(N)2'-regioselectivity. The N-Boc protecting group proved to be optimal as regards yields, reaction times and regioselectivities.

引用

页码：869 / 873

页数：5

共 31 条

[1] The reactivity of the N-Boc protecting group:: an underrated feature [J].

Agami, C ;

Couty, F .

TETRAHEDRON, 2002, 58 (14) :2701-2724

[2] Highly stereoselective synthesis of aristeromycin through dihydroxylation of 4-aryl-L-azido-2-cyclopentenes [J].

Ainai, T ;

Wang, YG ;

Tokoro, Y ;

Kobayashi, Y .

JOURNAL OF ORGANIC CHEMISTRY, 2004, 69 (03) :655-659

[3] Rhodium-catalyzed asymmetric arylative ring opening of bicyclic hydrazines [J].

Bertolini, Ferruccio ;

Macchia, Franco ;

Pineschi, Mauro .

TETRAHEDRON LETTERS, 2006, 47 (52) :9173-9176

[4] Highly functionalized cyclopentanes from meso bicyclic hydrazines. A rapid access to mannosidase inhibitors [J].

Bournaud, C ;

Robic, D ;

Bonin, M ;

Micouin, L .

JOURNAL OF ORGANIC CHEMISTRY, 2005, 70 (08) :3316-3317

[5] On the use of phosphoramidite ligands in copper-catalyzed asymmetric transformations with trialkylaluminum reagents [J].

Bournaud, Chloee ;

Falciola, Caroline ;

Lecourt, Thomas ;

Rosset, Stephane ;

Alexakis, Alexandre ;

Micouin, Laurent .

ORGANIC LETTERS, 2006, 8 (16) :3581-3584

[6]

Breit B, 2002, MODERN ORGANOCOPPER CHEMISTRY, P188, DOI 10.1002/3527600086.ch6

[7]

Breit B, 2001, ADV SYNTH CATAL, V343, P429, DOI 10.1002/1615-4169(200107)343:5<429::AID-ADSC429>3.0.CO

[8]

2-K

[9]

CHUNG CYJ, 1972, CAN J CHEMISTRY, V50, P1568

[10] New developments in the enantioselective synthesis of cyclopentyl carbocyclic nucleosides [J].

Crimmins, MT .

TETRAHEDRON, 1998, 54 (32) :9229-9272

← 1 2 3 4 →