caa a22 4500 378923072 CHVBK 20180305123610.0 cr unu---uuuuu 161128e20040101xx s 000 0 eng 10.1351/pac200476030625 doi (NATIONALLICENCE)gruyter-10.1351/pac200476030625 New insights into the mechanism of molybdenum-catalyzed asymmetric alkylation [Elektronische Daten] [S. W. Krska, D. L. Hughes, R. A. Reamer, D. J. Mathre, M. Palucki, Nobuyoshi Yasuda, Y. Sun, B. M. Trost] The major features of the catalytic cycle, including structures of key intermediates, have been determined for the molybdenum-catalyzed asymmetric alkylation. The crystal structure of the π-allyl intermediate exhibits 3-point binding of an anionic ligand. Based on NMR analysis, this species adopts in solution a structure consistent with that observed in the solid state. For the allylic alkylation, the crystal structure predicts the opposite stereochemistry vs. that observed experimentally, which suggests that either the reaction proceeds via a minor isomer (Curtin-Hammett conditions) or with retention of configuration. In addition, CO transfer, promoted by Mo(CO)6, has been found to play a key role in catalyst turnover. © 2013 Walter de Gruyter GmbH, Berlin/Boston Krska S. W. Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut Hughes D. L. Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut Reamer R. A. Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut Mathre D. J. Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut Palucki M. Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut Yasuda Nobuyoshi Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut Sun Y. Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut Trost B. M. Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut Pure and Applied Chemistry De Gruyter 76/3(2004-01-01), 625-633 0033-4545 76:3<625 2004 76 pac https://doi.org/10.1351/pac200476030625 text/html Onlinezugriff via DOI 1 research article jats NATIONALLICENCE 856 40 https://doi.org/10.1351/pac200476030625 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Krska S. W. Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut NATIONALLICENCE 700 1- Hughes D. L. Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut NATIONALLICENCE 700 1- Reamer R. A. Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut NATIONALLICENCE 700 1- Mathre D. J. Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut NATIONALLICENCE 700 1- Palucki M. Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut NATIONALLICENCE 700 1- Yasuda Nobuyoshi Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut NATIONALLICENCE 700 1- Sun Y. Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut NATIONALLICENCE 700 1- Trost B. M. Department of Process Research, Merck and Co., Inc., Rahway, NJ 07065, USA; Department of Chemistry, Stanford University, Palo Alto, CA 94305-5080, USA aut NATIONALLICENCE 773 0- Pure and Applied Chemistry De Gruyter 76/3(2004-01-01), 625-633 0033-4545 76:3<625 2004 76 pac CC0 http://creativecommons.org/publicdomain/zero/1.0 nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-gruyter