Diastereoselective Synthesis of Eight-Membered-Ring Allenes from Propargylic Epoxides and Aldehydes by Silylene Insertion into Carbon–Oxygen Bonds†
Christina Z. Rotsides
Department of Chemistry, New York University, 100 Washington Square East, New York, NY 10003 (USA)
Search for more papers by this authorDr. Chunhua Hu
Department of Chemistry, New York University, 100 Washington Square East, New York, NY 10003 (USA)
Search for more papers by this authorCorresponding Author
Prof. K. A. Woerpel
Department of Chemistry, New York University, 100 Washington Square East, New York, NY 10003 (USA)
Department of Chemistry, New York University, 100 Washington Square East, New York, NY 10003 (USA)===Search for more papers by this authorChristina Z. Rotsides
Department of Chemistry, New York University, 100 Washington Square East, New York, NY 10003 (USA)
Search for more papers by this authorDr. Chunhua Hu
Department of Chemistry, New York University, 100 Washington Square East, New York, NY 10003 (USA)
Search for more papers by this authorCorresponding Author
Prof. K. A. Woerpel
Department of Chemistry, New York University, 100 Washington Square East, New York, NY 10003 (USA)
Department of Chemistry, New York University, 100 Washington Square East, New York, NY 10003 (USA)===Search for more papers by this authorThe authors thank New York University and the Margaret and Herman Sokol Fellowship (to C.Z.R.) for support of this research. We thank the NYU Molecular Design Institute for the purchase of the Bruker SMART APEXII diffractometer.
Graphical Abstract
Bent out of shape: Silver-catalyzed insertions of silylenes into propargylic CO bonds of epoxides regioselectively form 1,2-silaoxetanes, which add to aldehydes to give the title allenes as single diastereomers (see scheme; Ts=4-toluenesulfonyl). An X-ray crystal structure confirmed the stereochemistry of the allene, which is bent significantly from linearity (164°).
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