| Title | Investigating the Nature of Palladium Chain-Walking in the Enantioselective Redox-Relay Heck Reaction of Alkenyl Alcohols |
| Authors | Hilton, Margaret J. Xu, Li-Ping Norrby, Per-Ola Wu, Yun-Dong Wiest, Olaf Sigman, Matthew S. |
| Affiliation | Univ Utah, Dept Chem, Salt Lake City, UT 84112 USA. Peking Univ, Shenzhen Grad Sch, Lab Computat Chem & Drug Design, Lab Chem Genom, Shenzhen 518055, Peoples R China. AstraZeneca, Global Med Dev, Pharmaceut Dev, SE-43183 Molndal, Sweden. Univ Notre Dame, Dept Chem & Biochem, Notre Dame, IN 46556 USA. Univ Utah, Dept Chem, 315 South 1400 East, Salt Lake City, UT 84112 USA. |
| Keywords | ARYLATIONS SELECTIVITY CATALYSTS STRATEGY |
| Issue Date | 2014 |
| Publisher | journal of organic chemistry |
| Citation | JOURNAL OF ORGANIC CHEMISTRY.2014,79,(24),11841-11850. |
| Abstract | The mechanism of the redox-relay Heck reaction was investigated using deuterium-labeled substrates. Results support a pathway through a low energy palladiumalkyl intermediate that immediately precedes product formation, ruling out a tautomerization mechanism. DFT calculations of the relevant transition structures at the M06/LAN2DZ+f/6-31+G* level of theory show that the former pathway is favored by 5.8 kcal/mol. Palladium chain-walking toward the alcohol, following successive beta-hydride eliminations and migratory insertions, is also supported in this study. The stereochemistry of deuterium labels is determined, lending support that the catalyst remains bound to the substrate during the relay process and that both cis- and trans-alkenes form from beta-hydride elimination. |
| URI | http://hdl.handle.net/20.500.11897/206922 |
| ISSN | 0022-3263 |
| DOI | 10.1021/jo501813d |
| Indexed | SCI(E) EI |
| Appears in Collections: | 深圳研究生院待认领 |
