Anti-Beckwith stereoselectivity in amidyl radical cyclisations: Bu3SnH-mediated 5-exo-trig acyl mode cyclisation of 2-substituted pent-4-enamide radicals
摘要:
2-Substituted amidyl radicals derived from 8a-d and 9a-d undergo acyl mode 5-exo-trig cyclisation to give 3,5-trans pyrrolidinones 11a-d and 14a-d as the major products in low diastereoselectivity (de = 9-36%). The steric nature of the nitrogen substituent attached to the amidyl radical does not have a significant effect on selectivity. The stereochemical outcome is opposite to that expected based upon applying the Beckwith rule. (C) 2013 Elsevier Ltd. All rights reserved.
[EN] MACROINITIATOR CONTAINING HYDROPHOBIC SEGMENT<br/>[FR] MACROINITIATEUR CONTENANT UN SEGMENT HYDROPHOBE
申请人:JOHNSON & JOHNSON VISION CARE
公开号:WO2012151134A1
公开(公告)日:2012-11-08
The present invention relates to macroinitiators comprising at least one hydrophobic segments in a molecule, wherein a molecular weight of the hydrophobic segment is 300 to 1800. The present invention further relates to block copolymers, wetting agent and polymeric materials having the block copolymers of the present invention associated with, which is suitable for medical devices, particularly for ophthalmic devices, including contact lenses, ophthalmic lenses, punctal plugs and artificial corneas.
Anti-Beckwith stereoselectivity in amidyl radical cyclisations: Bu3SnH-mediated 5-exo-trig acyl mode cyclisation of 2-substituted pent-4-enamide radicals
作者:Andrew J. Clark、Robert P. Filik、Gerard H. Thomas、John Sherringham
DOI:10.1016/j.tetlet.2013.05.109
日期:2013.7
2-Substituted amidyl radicals derived from 8a-d and 9a-d undergo acyl mode 5-exo-trig cyclisation to give 3,5-trans pyrrolidinones 11a-d and 14a-d as the major products in low diastereoselectivity (de = 9-36%). The steric nature of the nitrogen substituent attached to the amidyl radical does not have a significant effect on selectivity. The stereochemical outcome is opposite to that expected based upon applying the Beckwith rule. (C) 2013 Elsevier Ltd. All rights reserved.