Department of Chemistry, Boston College, Chestnut Hill, MA 02467-3860, USA.
Angew Chem Int Ed Engl. 2011 Aug 22;50(35):8167-71. doi: 10.1002/anie.201103470. Epub 2011 Jul 7.
Ex-changing places: a highly enantioselective desymmetrization of 1,2-diols has been developed in which the catalyst utilizes reversible covalent bonding to the substrate to achieve both high selectivity and rate acceleration (see scheme, PMP=pentalmethylpiperidine, TBS=tert-butyldimethylsilyl). Induced intramolecularity is responsible for the enhanced rate, thus allowing the reaction to be performed at room temperature.
开发出一种高度对映选择性的 1,2-二醇去对称化反应,其中催化剂利用与底物的可逆共价键合来实现高选择性和速率加速(见方案,PMP=五甲基哌啶,TBS=叔丁基二甲基硅基)。诱导的分子内性是提高速率的原因,从而使反应能够在室温下进行。