Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 59, Issue 34, Pages 14647-14655Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202006237
Keywords
allylic substitution; asymmetric catalysis; noncovalent interactions; palladium; statistical modeling
Categories
Funding
- National Institutes of Health [GM121383, R35 GM118190]
- Ministry of Science and Technology, Taiwan [106-2917-I-564-056]
- EU [789399]
- NSF [ACI-1548562]
- Marie Curie Actions (MSCA) [789399] Funding Source: Marie Curie Actions (MSCA)
Ask authors/readers for more resources
The mode of asymmetric induction in an enantioselective intramolecular allylic substitution reaction catalyzed by a combination of palladium and a chiral phosphoric acid was investigated by a combined experimental and statistical modeling approach. Experiments to probe nonlinear effects, the reactivity of deuterium-labeled substrates, and control experiments revealed that nucleophilic attack to the pi-allylpalladium intermediate is the enantio-determining step, in which the chiral phosphate anion is involved in stereoinduction. Using multivariable linear regression analysis, we determined that multiple noncovalent interactions with the chiral environment of the phosphate anion are integral to enantiocontrol in the transition state. The synthetic protocol to form chiral pyrrolidines was further applied to the asymmetric construction of C-O bonds at fully substituted carbon centers in the synthesis of chiral 2,2-disubstituted benzomorpholines.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available