Stereoselective chromium- and molybdenum-mediated transformations of arenes

Article Article scientifique Article Stereoselective chromium- and molybdenum-mediated transformations of arenes eng 2004 author Kundig Ernst Peter 26401 author Cannas Rita 109717 author Fabritius Charles-Henry Robert 537965 author Grossheimann Gabriele 113044 author Kandratenko M. author Laxmisha M. author Pache Sandrine 59445 author Ratni Hasane 503811 author Robvieux Fabrice 125761 author Romanens Patrick 22629 author Tchertchian Sylvie 508052 689-695 10.1351/pac200476030689 0033-4545 Tricarbonylchromium-mediated dearomatization provides a rapid access to substituted cyclohexadienes. Efficient asymmetric routes to planar chiral arene complexes and to substituted cyclohexadienes have been developed. The article sums up the main features of this chemistry. Highly enantiomerically enriched ortho-substituted benzaldehyde complexes are accessible via asymmetric lithiation followed by trapping with electrophiles. In different solvents, the trimethylsilyl complex exhibits [alpha] values ranging from −174 to +108 for the same enantiomer. Details of two asymmetric syntheses of natural products are given: the alkaloid lasubine I starting from a highly enantiomerically enriched planar chiral arene complex and the marine furanosesquiterpene acetoxytubipofuran. The latter is assembled via asymmetric dearomatization of a benzaldehyde imine complex. Other key steps include an Eschenmoser–Claisen rearrangement and a regio- and diastereoselective Pd-catalyzed allylic substitution. The final section deals with labile arene metal complexes. For the first time, dearomatization reactions mediated by the Mo(CO)3 group have been realized. The reactions show strong analogies to the Cr(CO)3-mediated reactions, but exhibit also marked differences: the arene–Mo bond is stronger, but more labile, and the sequential double additions show different selectivities compared to the chromium analogs. 12th International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS-12). - Toronto (Ontario, Canada). - 6–10 July 2003 Dewey 540 36 Département de chimie organique 141 false Pure and applied chemistry 76 3 ceb98f6d-c7d3-48ab-ad7b-c092b97bafc8 Article Restricted file1.pdf 263368 application/pdf restrictedAccess Faculté des sciences / Section de chimie et biochimie / Département de chimie organique

Title	Published in	Year	Views	Downloads

Synthesis of Substituted Arene Molybdenum Complexes by Arene Exchange	Organometallics	2004	739	0
Stereoselective chromium- and molybdenum-mediated transformations of arenes	Pure and applied chemistry	2004	707	0
trans-Addition of Two Carbon Substituents across a Benzene Double Bond in [(η6-Benzene)Mo(CO)>3>]	Angewandte Chemie	2002	683	0

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Fabritius, Charles-Henry Robert