Premium
Controlled Synthesis of α‐Allenic Ester and Spiro Ketone Derivatives from Tailored α‐Substituted Cycloalkanones Through Cascade Reactions: Exploring the Possible Reaction Pathways by Means of Semiempirical MO Calculations
Author(s) -
Mota Antonio J.,
Klein Aurélie,
Wendling Florence,
Dedieu Alain,
Miesch Michel
Publication year - 2005
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.200500339
Subject(s) - chemistry , bicyclic molecule , ketone , electrophile , cascade , cascade reaction , molecule , ring (chemistry) , stereochemistry , medicinal chemistry , organic chemistry , catalysis , chromatography
Functionalized bicyclic electrophilic allenes and (or) spiro ketones have been obtained through a cascade reaction when acetylenic ω‐keto esters were treated with tetra‐ n ‐butylammonium fluoride (TBAF). The isolated products can be modulated by using different starting materials (i.e. varying ring size, spacer length) and reaction times. The results indicate that these reactions take place under kinetic control. In line with this, a semiempirical study was carried out in order to determine the preferred reaction pathways and the preferred cis / trans conformation of the bicyclic allenic derivatives. An excellent correlation was found between theoretical and experimental results, and the whole process dramatically depends on the presence of the HF molecule. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)