远程立体诱导全取代烯醇盐的酰化反应：硅基乙二醛酸酯和β-内酰胺的串联 Reformatsky/季碳 Claisen 缩合反应。
Remote stereoinduction in the acylation of fully substituted enolates: tandem Reformatsky/quaternary Claisen condensations of silyl glyoxylates and β-lactones.
机构信息
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, USA.
出版信息
J Am Chem Soc. 2010 Dec 15;132(49):17393-5. doi: 10.1021/ja108848d. Epub 2010 Nov 18.
Abstract
Reformatsky reagents react sequentially with silyl glyoxylates and β-lactones to give highly functionalized Claisen condensation products. A heretofore undocumented instance of stereochemical 1,4-induction results in efficient transmission of β-lactone stereochemistry to the emerging fully substituted stereocenter. Second-stage transformations reveal that the five heteroatom-containing functionalities embedded within the products are entirely chemo-differentiated, a circumstance that permits rapid assembly of the leustroducsin B core substructure.
摘要
Reformatsky 试剂与硅基乙二醛和β-内酰胺依次反应，生成高度官能化的 Claisen 缩合产物。本文报道了首例立体化学 1,4-诱导的实例，β-内酰胺的立体化学能够高效地传递到新生成的完全取代的立体中心。第二阶段的转化表明，产物中嵌入的五个杂原子官能团完全具有化学差异性，这种情况允许快速组装雷杜辛 B 核心亚结构。
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