Quantifying Structural Effects of Amino Acid Ligands in Pd(II)-Catalyzed Enantioselective C–H Functionalization Reactions
| Autor: | Yoonsu Park, Matthew S. Sigman, Zachary L. Niemeyer, Jin-Quan Yu |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
chemistry.chemical_classification
010405 organic chemistry Chemistry Ligand Stereochemistry Organic Chemistry Enantioselective synthesis Alkylation Dihedral angle 010402 general chemistry 01 natural sciences Combinatorial chemistry 0104 chemical sciences Catalysis Amino acid Inorganic Chemistry Side chain Physical and Theoretical Chemistry Protecting group |
| Zdroj: | Organometallics. 37:203-210 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/acs.organomet.7b00751 |
| Popis: | Delineating complex ligand effects on enantioselectivity is a longstanding challenge in asymmetric catalysis. With α-amino acid ligands, the essential difficulty lies in accurately describing integrated perturbations induced by simultaneous variation about the α side chain and N protecting group of the ligand, which hampers an intuitive understanding of the structure–enantioselectivity relationships. To deconvolute such complexity in chiral amino acid enabled enantioselective C–H functionalization reactions, a computational organometallic model system was developed. Whereas a model based only on a conventional results in diminished predictive power, the ground state Pd(II)-based models display an excellent ability to describe the observed enantioselectivity. These structures were leveraged using a multivariate modeling approach to successfully describe Pd(II)-catalyzed C–H alkylation, alkenylation, and two C–H arylation reactions, wherein descriptors of torsion angle, percent buried volume, and NBO charge... |
| Databáze: | OpenAIRE |
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