Warren and Katharine Schlinger Laboratory for Chemistry and Chemical Engineering, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, 91125, USA.
Angew Chem Int Ed Engl. 2011 Mar 14;50(12):2756-60. doi: 10.1002/anie.201007814. Epub 2011 Feb 24.
A simple protocol for the practical, scalable, catalytic asymmetric synthesis of γ-quaternary acylcyclopentenes in up to 91% overall yield and 92% ee has been developed. The reaction sequence employs a palladium-catalyzed enantioselective alkylation reaction and exploits the unusual stability of β-hydroxy cycloheptanones to achieve a general and robust method for performing two-carbon ring contractions. The resulting enantioenriched, highly-functionalized acylcyclopentenes provide a variable substituent and four additional functional group handles for chemoselective manipulation and potential application to the total synthesis of a wide array of natural products.
已经开发出一种用于实用、可扩展、催化不对称合成γ-季戊酰基环戊烯的简单方案，总收率高达 91%，对映体过量值高达 92%。该反应序列采用钯催化的对映选择性烷基化反应，并利用β-羟基环己酮的不寻常稳定性实现了一种通用且强大的方法，用于进行两碳环收缩。所得的对映体富集、高度官能化的酰基环戊烯提供了一个可变取代基和四个额外的官能团，用于选择性化学操作，并有可能应用于广泛的天然产物的全合成。
