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Removable Silyl Group as a “Masked Proton” in Oxy‐2‐oxonia(azonia)‐Cope Rearrangement: Applications in Stereoselective Total Synthesis of Natural Macrolides
Author(s) -
Mu Wenbo,
Zou Yue,
Zhou Lijun,
Wang Quanrui,
Goeke Andreas
Publication year - 2015
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201500654
Subject(s) - chemistry , stereoselectivity , silylation , ring (chemistry) , nucleophilic addition , lewis acids and bases , nucleophile , trimethylsilyl , stereochemistry , total synthesis , medicinal chemistry , organic chemistry , catalysis
In the presence of a Lewis acid, trimethylsilyl‐substituted β,γ‐unsaturated ketones and aldehydes (imines) undergo nucleophilic addition to produce zwitterionic intermediates, followed by oxy‐2‐oxonia(azonia)‐Cope rearrangements to give homoallylic esters (amides). In the case of TMS‐containing 2‐vinylcycloalkanones, the process results in ring‐enlargement, providing 10‐ to 16‐membered lactones. This protocol was applied to the total synthesis of ( R )‐phoracantholide I.