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A Convenient Road to 1‐Chloropentacycloundecanes – A Joint Experimental and Computational Investigation
Author(s) -
Sharapa Dmitry I.,
Gayday Alexander V.,
Mitlenko Alena G.,
Levandovskiy Igor A.,
Shubina Tatyana E.
Publication year - 2011
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.201001731
Subject(s) - chemistry , regioselectivity , reaction mechanism , mechanism (biology) , computational chemistry , diketone , catalysis , stereochemistry , organic chemistry , physics , quantum mechanics
An efficient synthetic strategy to obtain 1‐chloro‐ C s ‐trishomocubane and 1‐chloro‐ D 3 ‐trishomocubane is described. 1‐Chloro‐ C s ‐trishomocubane is synthesized by a regioselective Diels–Alder reaction, and B3PW91/6‐31G(d,p) calculations offer a plausible explanation of the reaction mechanism. Surprisingly, 1‐chloro‐ C s ‐trishomocubane does not undergo an acid‐catalyzed rearrangement to form 1‐chloro‐ D 3 ‐trishomocubane and was obtained by chlorosulfation of Cookson's diketone. A possible mechanism of the reaction involving the formation of C s ‐ and D 3 ‐trishomocubane nonclassical cations was proposed on the basis of a mechanistic [B3PW91/6‐31G(d,p) and MP2/cc‐pVDZ] study.