Journal
CHEMICAL SCIENCE
Volume 8, Issue 8, Pages 5746-5756Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7sc01674c
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Funding
- NSF under the CCI Center for Selective C-H Functionalization (CCHF) [CHE-1205646]
- University of Chicago Louis Block Fund
- NSF [DGE-1144082]
- University of Chicago Department of Chemistry
- NSF MRI-R2 grant [CHE-0958205]
- U.S. DOE [DE-AC02-06-CH11357]
- Division of Chemistry (CHE), National Science Foundation [NSF/CHE-1346572]
- Division of Materials Research (DMR), National Science Foundation [NSF/CHE-1346572]
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [1205646] Funding Source: National Science Foundation
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Mono-protected amino acid (MPAA) ligands are used in a number of Pd-catalyzed C-H functionalization reactions. MPAAs have been proposed to bind to Pd(II) via kappa(2)-(N, O) coordination, but such binding has not yet been experimentally validated. Herein, we report the synthesis and detailed characterization of a series of MPAA complexes prepared via cyclopalladation of dimethylbenzylamine in the presence of MPAAs. The isolated complexes exist as m-carboxylato (MPAA) bridged dimers and feature potential M-M cooperativity and secondary sphere hydrogen bonding. Selective MPAA coordination and relay of stereochemistry, previously suggested to uniquely result from kappa(2)-(N, O) MPAA coordination, are both observed. The isolated MPAA complexes undergo C-C and C-X (X = Cl, Br, I) bond formation when treated with electrophiles used for catalytic C-H functionalization. Stoichiometric iodination of MPAA palladacycles was found to proceed via a dinuclear palladium species with one equivalent of iodine in the rate limiting transition structure, and the isolated complexes also served as viable precatalysts for catalytic C-H functionalization. Together, these results provide a number of insights into the reactivity of Pd-MPAA complexes relevant to C-H bond functionalization.
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