Condensation Oligomers with Sequence Control but without Coupling Reagents and Protecting Groups via Asymmetric Hydroformylation and Hydroacyloxylation
Condensation Oligomers with Sequence Control but without Coupling Reagents and Protecting Groups via Asymmetric Hydroformylation and Hydroacyloxylation
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DOI：
10.1021/acs.joc.6b02210
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发表时间：
2016-11-18
影响因子：
3.6
通讯作者：
Landis, Clark R.
中科院分区：
文献类型：
--
作者：
Foarta, Floriana;Landis, Clark R.
描述了一种新的策略，不需要偶联试剂和保护/去保护步骤，用于合成含有多达四个单体单元的低聚（2-羟基酸），具有原子经济性，序列特异性和立体中心构型控制。该策略包括不对称氢甲酰化/氧化/炔氢酰基化序列的迭代应用，具有催化、原子经济的C-C和C-O键形成反应。不对称氢甲酰化与铑-二氮磷烷催化剂引入每个立体中心高对映-（约93% e.e），非对映-（高达25:1 d.r）和区域选择性（>50:1）在低催化剂负载和温和的压力。每个单体的侧链都是通过选择各种现成的炔来定制的。
A novel strategy, free of coupling reagents and protection/deprotection steps, for the synthesis of oligo(2-hydroxyacid)s containing up to four monomer units with atom economy, sequence specificity, and control of stereocenter configuration is described. The strategy comprises an iterative application of the sequence asymmetric hydroformylation/ oxidation/alkyne hydroacyloxylation that features catalytic, atom-economical C-C and C-O bond forming reactions. Asymmetric hydroformylation with Rh-bisdiazaphospholane catalyst introduces each stereocenter with high enantio- (ca. 93% e.e.), diastereo- (up to 25:1 d.r.), and regioselectivity (>50:1) at low catalyst loadings and mild pressures. The side chain in each monomer is tailored by choosing from a variety of readily available alkynes.