Tang Fan, Yao Yun, Xu Yan-Jun, Lu Chong-Dao
Key Laboratory of Plant Resources and Chemistry of Arid Zones, Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, No. 40-1 South Beijing Road, Urumqi, 830011, China.
University of Chinese Academy of Sciences, Beijing, 100049, China.
Angew Chem Int Ed Engl. 2018 Nov 19;57(47):15583-15586. doi: 10.1002/anie.201809551. Epub 2018 Oct 24.
A diastereoselective [2,3] rearrangement of O-silyl N-sulfinyl N,O-ketene acetals derived from chiral N-acyl tert-butanesulfinamides was developed, giving α-sulfenyloxy carboxamides with excellent enantioselectivity. Enolization and subsequent silylation of N-acyl tert-butanesulfinamides initiate this aza variant of the Mislow-Evans rearrangement, in which the chirality at the sulfur atom in the rearrangement precursors is faithfully transferred to the α-carbon stereocenter of the products. The Ellman sulfinamide, often used as a chiral ammonia equivalent, can serve in this rearrangement as a chiral precursor for the asymmetric synthesis of α-oxygen-functionalized carboxamides.
我们开发了一种由手性N-酰基叔丁基亚磺酰胺衍生的O-硅基N-亚磺酰基N,O-乙烯酮缩醛的非对映选择性[2,3]重排反应，可得到对映选择性优异的α-亚磺酰氧基羧酰胺。N-酰基叔丁基亚磺酰胺的烯醇化及随后的硅烷化引发了这种米斯洛-埃文斯重排反应的氮杂变体，其中重排前体中硫原子的手性被忠实地转移至产物的α-碳立体中心。常用于作为手性氨等效物的埃尔曼亚磺酰胺，在该重排反应中可作为用于不对称合成α-氧官能化羧酰胺的手性前体。
