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Synthesis of Highly Substituted Cyclobutane Fused‐Ring Systems from N ‐Vinyl β‐Lactams through a One‐Pot Domino Process
Author(s) -
Cheung Lawrence L. W.,
Yudin Andrei K.
Publication year - 2010
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200902748
Subject(s) - cyclobutane , sigmatropic reaction , chemistry , ring (chemistry) , domino , limiting , cascade reaction , stereochemistry , cope rearrangement , combinatorial chemistry , organic chemistry , catalysis , mechanical engineering , engineering
In this contribution, aminocyclobutanes, as well as eight‐membered enamide rings, have been made from N ‐vinyl β‐lactams. The eight‐membered products have been formed by a [3,3]‐sigmatropic rearrangement, whereas the aminocyclobutanes have been derived from a domino [3,3]‐rearrangement/6π‐electrocyclisation process. The aminocyclobutanes have been obtained in a highly diastereoselective fashion. The cyclobutane ring system tolerates fusion even if adjacent quaternary centres are present. Systems containing up to four fused rings are readily accessible. The reaction profile has been investigated by using Gaussian 03. This study suggests that two reaction pathways for aminocyclobutane formation are possible. In one pathway the [3,3]‐sigmatropic rearrangement is the rate‐limiting step and in the second pathway the electrocyclisation is rate limiting. Taken together, these reactions should facilitate the construction of fused heterocycles.