An asymmetric Kharasch reaction mediated by D-xylose: long range diastereocontrol

被引：12

作者：

Enholm, EJ ^{[1
]}

Bhardawaj, A ^{[1
]}

机构：

[1] Univ Florida, Dept Chem, Gainesville, FL 32611 USA

来源：

TETRAHEDRON LETTERS | 2003年 / 44卷 / 19期

基金：

美国国家科学基金会;

关键词：

free radical; diastereoselective; atom transfer; Kharasch reaction;

D O I：

10.1016/S0040-4039(03)00756-1

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

An asymmetric Kharasch-type atom transfer reaction was studied under 13 different sets of reaction conditions in order to obtain the highest levels of diastereoselection. The highest ratio of 12.5:1 (71%) was observed at low temperatures (-78degreesC) using the Lewis acid Eu(OTf)(3). Because the new asymmetric center is so distant from the D-xylose, we propose a transition state involving two sugars. The conversion of the major product to a naturally occurring chiral gamma-butyrolactone, under basic conditions, is described which also confirmed the diastereoselectivity and absolute stereochemistry of the Kharasch reaction. (C) 2003 Elsevier Science Ltd. All rights reserved.

引用

页码：3763 / 3765

页数：3

共 35 条

[1] Asymmetric catalysis .108. Copper catalysts with optically active ligands in the enantioselective Meerwein arylation of activated olefins
Brunner, H
Bluchel, C
Doyle, MP
[J]. JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1997, 541 (1-2) : 89 - 95
[2] ARE RELATIVE BOND-ENERGIES A MEASURE OF RADICAL STABILIZATION ENERGIES
CLARK, KB
WAYNER, DDM
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (24) : 9363 - 9365
[3] ATOM TRANSFER ADDITION, ANNULATION, AND MACROCYCLIZATION REACTIONS OF IODOMALONONITRILES
CURRAN, DP
SEONG, CM
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (25) : 9401 - 9403
[4] ATOM TRANSFER ADDITION AND ANNULATION REACTIONS OF IODOMALONATES
CURRAN, DP
CHEN, MH
SPLETZER, E
SEONG, CM
CHANG, CT
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (24) : 8872 - 8878
[5] RATE CONSTANTS FOR HALOGEN ATOM TRANSFER FROM REPRESENTATIVE ALPHA-HALOCARBONYL COMPOUNDS TO PRIMARY ALKYL RADICALS
CURRAN, DP
BOSCH, E
KAPLAN, J
NEWCOMB, M
[J]. JOURNAL OF ORGANIC CHEMISTRY, 1989, 54 (08) : 1826 - 1831
[6] THE DESIGN AND APPLICATION OF FREE-RADICAL CHAIN REACTIONS IN ORGANIC-SYNTHESIS .2.
CURRAN, DP
[J]. SYNTHESIS-STUTTGART, 1988, (07): : 489 - 513
[7] Highly diastereoselective 5-hexenyl radical cyclizations with Lewis acids and carbohydrate scaffolds
Enholm, EJ
Cottone, JS
Allais, F
[J]. ORGANIC LETTERS, 2001, 3 (02) : 145 - 147
[8] Free radical allyl transfers utilizing soluble non-cross-linked polystyrene and carbohydrate scaffold supports
Enholm, EJ
Gallagher, ME
Jiang, SJ
Batson, WA
[J]. ORGANIC LETTERS, 2000, 2 (21) : 3355 - 3357
[9] Lewis acid-promoted Kharasch-Curran additions:: A competition kinetics study of bromine atom transfer addition of N-α-bromoacetyl-oxazolidinone to 1-hexene
Feng, H
Kavrakova, IK
Pratt, DA
Tellinghuisen, J
Porter, NA
[J]. JOURNAL OF ORGANIC CHEMISTRY, 2002, 67 (17) : 6050 - 6054
[10] Stereoselective radical carbon-carbon bond forming reactions of beta-alkoxy esters: Atom and group transfer allylations under bidentate chelation controlled conditions
Guindon, Y
Guerin, B
Chabot, C
Ogilvie, W
[J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (50) : 12528 - 12535

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