caa a22 4500 378923188 CHVBK 20200916193718.0 cr unu---uuuuu 161128e20040101xx s 000 0 eng 10.1351/pac200476030689 doi (NATIONALLICENCE)gruyter-10.1351/pac200476030689 Stereoselective chromium- and molybdenum-mediated transformations of arenes [Elektronische Daten] [E. P. Kündig, Rita Cannas, C.-H. Fabritius, Gabriele Grossheimann, Mikhail Kondratenko, Mundruppady Laxmisha, S. Pache, H. Ratni, F. Robvieux, P. Romanens, S. Tchertchian] 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. © 2013 Walter de Gruyter GmbH, Berlin/Boston Kündig E. P. Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut Cannas Rita Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut Fabritius C.-H Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut Grossheimann Gabriele Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut Kondratenko Mikhail Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut Laxmisha Mundruppady Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut Pache S. Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut Ratni H. Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut Robvieux F. Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut Romanens P. Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut Tchertchian S. Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut Pure and Applied Chemistry De Gruyter 76/3(2004-01-01), 689-695 0033-4545 76:3<689 2004 76 pac https://doi.org/10.1351/pac200476030689 text/html Onlinezugriff via DOI BK010053 XK010053 XK010000 CC0 http://creativecommons.org/publicdomain/zero/1.0 nationallicence 1 research article jats NATIONALLICENCE NATIONALLICENCE NL-gruyter NATIONALLICENCE 856 40 https://doi.org/10.1351/pac200476030689 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Kündig E. P. Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut NATIONALLICENCE 700 1- Cannas Rita Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut NATIONALLICENCE 700 1- Fabritius C.-H Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut NATIONALLICENCE 700 1- Grossheimann Gabriele Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut NATIONALLICENCE 700 1- Kondratenko Mikhail Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut NATIONALLICENCE 700 1- Laxmisha Mundruppady Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut NATIONALLICENCE 700 1- Pache S. Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut NATIONALLICENCE 700 1- Ratni H. Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut NATIONALLICENCE 700 1- Robvieux F. Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut NATIONALLICENCE 700 1- Romanens P. Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut NATIONALLICENCE 700 1- Tchertchian S. Department of Organic Chemistry, University of Geneva, 30 Quai Ernest, Ansermet, 1211 Geneva 4, Switzerland aut NATIONALLICENCE 773 0- Pure and Applied Chemistry De Gruyter 76/3(2004-01-01), 689-695 0033-4545 76:3<689 2004 76 pac