Phase-transfer-catalysed asymmetric synthesis of tetrasubstituted allenes
Phase-transfer-catalysed asymmetric synthesis of tetrasubstituted allenes
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DOI：
10.1038/nchem.1567
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发表时间：
2013-03-01
期刊：
影响因子：
21.8
通讯作者：
Maruoka, Keiji
中科院分区：
文献类型：
--
作者：
Hashimoto, Takuya;Sakata, Kazuki;Maruoka, Keiji
丙二烯是基于通过两个累积的碳-碳双键连接的三个碳的分子。鉴于其轴向手性和独特的反应性，取代丙二烯在有机化学中作为关键合成中间体和直接作为生物活性化合物的一部分具有多种应用。尽管对这些的需求促使许多人努力通过不对称催化来制造轴向手性、取代的丙二烯，但完全取代的丙二烯（四取代丙二烯）的催化不对称合成在很大程度上仍然是一个未解决的问题。解决这一难题的根本障碍是缺乏在催化作用下提供四取代丙二烯的简单合成转化。我们在此报告了一种克服这一问题的策略，通过使用 1-烷基联烯-1,3-二羧酸酯与 N-芳基磺酰亚胺以及苄基和烯丙基溴的相转移催化不对称官能化。
Allenes are molecules based on three carbons connected by two cumulated carbon-carbon double bonds. Given their axially chiral nature and unique reactivity, substituted allenes have a variety of applications in organic chemistry as key synthetic intermediates and directly as part of biologically active compounds. Although the demands for these motivated many endeavours to make axially chiral, substituted allenes by exercising asymmetric catalysis, the catalytic asymmetric synthesis of fully substituted ones (tetrasubstituted allenes) remained largely an unsolved issue. The fundamental obstacle to solving this conundrum is the lack of a simple synthetic transformation that provides tetrasubstituted allenes in the action of catalysis. We report herein a strategy to overcome this issue by the use of a phase-transfer-catalysed asymmetric functionalization of 1-alkylallene-1,3-dicarboxylates with N-arylsulfonyl imines and benzylic and allylic bromides.