通过 1,3-环己二烯与手性β-硝基丙烯酸酯的[4+2]环加成反应合成手性反式-N-Boc-3-氨基双环[2.2.2]辛烷-2-羧酸及其双环 1,3-氨基醇衍生物。

Synthesis of enantiopure trans-N-Boc-3-aminobicyclo[2.2.2]octane-2-carboxylic acids and their bicyclic 1,3-amino alcohol derivatives via the [4+2] cycloaddition of 1,3-cyclohexadiene to a chiral β-nitroacrylate.

机构信息

Institut des Biomolécules Max Mousseron (IBMM) UMR 5247 CNRS-UM1-UM2, Université Montpellier 2, Bâtiment Chimie (17), 34095 Montpellier cedex 5, France.

出版信息

Chirality. 2011 Mar;23(3):245-9. doi: 10.1002/chir.20906. Epub 2010 Oct 6.

DOI:10.1002/chir.20906

PMID:20928894

Abstract

The chiral β-nitroacrylate 2 derived from the (R)- or (S)-4-(3-hydroxy-4,4-dimethyl-2-oxopyrrolidin-1-yl) benzoic acid 1 acts as a reactive dienophile in a diastereoselective Diels-Alder reaction with 1,3-cyclohexadiene. The major cycloadducts have been isolated and transformed into enantiopure trans(2S,3S)- or (2R,3R)-N-Boc-3-aminobicyclic[2,2,2]octane-2-carboxylic acids 5. The trans-(2S,3S)- or (2R,3R)-N-Boc 3-(hydoxymethyl)-2-aminobicyclic[2,2,2]octane 6 derivatives were also obtained.

摘要

(R)-或(S)-4-(3-羟基-4,4-二甲基-2-氧代吡咯烷-1-基)苯甲酸 1 衍生的手性β-硝基丙烯酸酯 2 作为一个反应性二烯亲二烯体，在立体选择性 Diels-Alder 反应中与 1,3-环己二烯反应。主要的环加成产物已经被分离出来，并转化为对映体纯的反式(2S,3S)-或(2R,3R)-N-Boc-3-氨基双环[2,2,2]辛烷-2-羧酸 5。还得到了反式-(2S,3S)-或(2R,3R)-N-Boc 3-(羟甲基)-2-氨基双环[2,2,2]辛烷 6 衍生物。