Torsional Steering Controls the Stereoselectivity of Epoxidation in the Guanacastepene A Synthesis
- 21 March 2006
- journal article
- letter
- Published by American Chemical Society (ACS) in Organic Letters
- Vol. 8 (8) , 1513-1516
- https://doi.org/10.1021/ol052862g
Abstract
The stereoselectivity of the key epoxidation step in the synthesis of guanacastepene A is shown to be controlled by torsional steering. In this particular epoxidation reaction, the transition structure energetic difference is enhanced by the great asynchronicity of the forming C−O bonds that intensifies the torsional interactions.Keywords
This publication has 20 references indexed in Scilit:
- Total Synthesis of Guanacastepene A: A Route to Enantiomeric ControlThe Journal of Organic Chemistry, 2005
- Transition States and Origins of Stereoselectivity of Epoxidations by Oxaziridinium SaltsJournal of the American Chemical Society, 2000
- Torsional and Steric Effects Control the Stereoselectivities of Alkylations of Pyrrolidinone EnolatesJournal of the American Chemical Society, 1999
- Experimental Geometry of the Epoxidation Transition StateJournal of the American Chemical Society, 1997
- Stereoselective Epoxidations and Electrophilic Additions to Partial Ergot Alkaloids and Conformationally-Fixed Styrenes. Experimental and Theoretical Modeling Evidence for the Importance of Torsional Steering as a Stereocontrol ElementThe Journal of Organic Chemistry, 1994
- Quantitative modeling of proximity effects on organic reactivityAccounts of Chemical Research, 1990
- Origin of enhanced axial attack by sterically undemanding nucleophiles on cyclohexenonesJournal of the American Chemical Society, 1987
- Torsional and steric control of stereoselectivity in isodicyclopentadiene cycloadditionsJournal of the American Chemical Society, 1985
- Origin of Huisgen's factor x: staggering of allylic bonds promotes anomalously rapid exo attack on norbornenesJournal of the American Chemical Society, 1982
- Bicyclo[3.1.0]hexane conformation. Crystal structure of N-exo-6-bicyclo[3.1.0]hexyl-p-bromosulfonamideThe Journal of Organic Chemistry, 1971