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Why is copper(I) complex more competent than dirhodium(II) complex in catalytic asymmetric O-H insertion reactions? A computational study of the metal carbenoid O-H insertion into water.
J Am Chem Soc. 2009 Dec 16; 131(49):17783-5.JA

Abstract

The asymmetric O-H insertion reaction is an ideal synthetic strategy for preparing optically pure alpha-alkoxy, alpha-aryloxy, and alpha-hydroxy carboxylic acid derivatives, which are valuable building blocks for the construction of natural products and other biologically active molecules. Surprisingly, to date there have been no reports of significant levels of enantiocontrol in the O-H insertions using chiral dirhodium(II) catalysts, which are powerful for asymmetric C-H insertions. Only recently, through the use of chiral copper catalysts, have highly enantioselective insertions of alpha-diazocarbonyl compounds into O-H bonds been achieved. To explain these interesting phenomena, density functional theory calculations have been conducted. The results show that in the Cu(I)-catalyzed system, the [1,2]-H shift process (the stereocenter formation step) favors the copper-associated ylide pathway. This ensures that when a chiral copper complex is used as the catalyst, the stereocenter forms in a chiral environment, which is the prerequisite for achieving enantioselectivity. In contrast, the free-ylide pathway is favored in the Rh(II)-catalyzed system. This significant difference renders the copper(I) complexes more competent than the dirhodium(II) complexes in catalytic asymmetric O-H insertions. In addition, it has been found for the first time that in transition-metal-catalyzed X-H insertions, water acts as an efficient proton-transport catalyst for the [1,2]-H shift.

Authors+Show Affiliations

Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China.No affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

19924864

Citation

Liang, Yong, et al. "Why Is copper(I) Complex More Competent Than dirhodium(II) Complex in Catalytic Asymmetric O-H Insertion Reactions? a Computational Study of the Metal Carbenoid O-H Insertion Into Water." Journal of the American Chemical Society, vol. 131, no. 49, 2009, pp. 17783-5.
Liang Y, Zhou H, Yu ZX. Why is copper(I) complex more competent than dirhodium(II) complex in catalytic asymmetric O-H insertion reactions? A computational study of the metal carbenoid O-H insertion into water. J Am Chem Soc. 2009;131(49):17783-5.
Liang, Y., Zhou, H., & Yu, Z. X. (2009). Why is copper(I) complex more competent than dirhodium(II) complex in catalytic asymmetric O-H insertion reactions? A computational study of the metal carbenoid O-H insertion into water. Journal of the American Chemical Society, 131(49), 17783-5. https://doi.org/10.1021/ja9086566
Liang Y, Zhou H, Yu ZX. Why Is copper(I) Complex More Competent Than dirhodium(II) Complex in Catalytic Asymmetric O-H Insertion Reactions? a Computational Study of the Metal Carbenoid O-H Insertion Into Water. J Am Chem Soc. 2009 Dec 16;131(49):17783-5. PubMed PMID: 19924864.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Why is copper(I) complex more competent than dirhodium(II) complex in catalytic asymmetric O-H insertion reactions? A computational study of the metal carbenoid O-H insertion into water. AU - Liang,Yong, AU - Zhou,Haolai, AU - Yu,Zhi-Xiang, PY - 2009/11/21/entrez PY - 2009/11/21/pubmed PY - 2010/3/17/medline SP - 17783 EP - 5 JF - Journal of the American Chemical Society JO - J Am Chem Soc VL - 131 IS - 49 N2 - The asymmetric O-H insertion reaction is an ideal synthetic strategy for preparing optically pure alpha-alkoxy, alpha-aryloxy, and alpha-hydroxy carboxylic acid derivatives, which are valuable building blocks for the construction of natural products and other biologically active molecules. Surprisingly, to date there have been no reports of significant levels of enantiocontrol in the O-H insertions using chiral dirhodium(II) catalysts, which are powerful for asymmetric C-H insertions. Only recently, through the use of chiral copper catalysts, have highly enantioselective insertions of alpha-diazocarbonyl compounds into O-H bonds been achieved. To explain these interesting phenomena, density functional theory calculations have been conducted. The results show that in the Cu(I)-catalyzed system, the [1,2]-H shift process (the stereocenter formation step) favors the copper-associated ylide pathway. This ensures that when a chiral copper complex is used as the catalyst, the stereocenter forms in a chiral environment, which is the prerequisite for achieving enantioselectivity. In contrast, the free-ylide pathway is favored in the Rh(II)-catalyzed system. This significant difference renders the copper(I) complexes more competent than the dirhodium(II) complexes in catalytic asymmetric O-H insertions. In addition, it has been found for the first time that in transition-metal-catalyzed X-H insertions, water acts as an efficient proton-transport catalyst for the [1,2]-H shift. SN - 1520-5126 UR - https://www.unboundmedicine.com/medline/citation/19924864/Why_is_copper_I__complex_more_competent_than_dirhodium_II__complex_in_catalytic_asymmetric_O_H_insertion_reactions_A_computational_study_of_the_metal_carbenoid_O_H_insertion_into_water_ L2 - https://doi.org/10.1021/ja9086566 DB - PRIME DP - Unbound Medicine ER -