A practical asymmetric conjugate addition to cyclic enones with chiral bifunctional Ru amido catalysts

Pavel A. Dub; Hui Wang; Masahito Watanabe; Ilya D. Gridnev; Takao Ikariya

doi:10.1016/j.tetlet.2012.04.100

A practical asymmetric conjugate addition to cyclic enones with chiral bifunctional Ru amido catalysts

Pavel A. Dub, Hui Wang, Masahito Watanabe, Ilya D. Gridnev, Takao Ikariya

Research output: Contribution to journal › Article › peer-review

22 Citations (Scopus)

Abstract

A practical asymmetric C-C bond formation to synthetically useful β-chiral cyclic ketones (>99% ee) using bifunctional chiral amido Ru catalysts under an S/C = 1000, the highest ratio achieved so far in the literature for this class of reactions, is described. The catalytic reactivity decreases in the order of Ru(Msdpen)(hmb) > Ru(Pfbsdpen)(hmb) > Ru(Tsdpen)(hmb) > Ru(PMsdpen)(hmb), where Ru(Pfbsdpen)(hmb) is a newly developed chiral bifunctional catalyst. Complex Ru(Msdpen)(hmb) was identified as the best in terms of reactivity and enantioface selectivity, whereas Ru(PMsdpen)(hmb) gave unsatisfactory results. An importance of the NH proton in the bifunctional catalyst for determining the enantioselectivity has been experimentally demonstrated. Valuable information for the reaction mechanism was accumulated.

Original language	English
Pages (from-to)	3452-3455
Number of pages	4
Journal	Tetrahedron Letters
Volume	53
Issue number	27
DOIs	https://doi.org/10.1016/j.tetlet.2012.04.100
Publication status	Published - 2012 Jul 4
Externally published	Yes

Keywords

Asymmetric Michael addition
Bifunctional catalyst
C-C bond formation
Cyclic enone
Ru catalyst

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tetlet.2012.04.100

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title = "A practical asymmetric conjugate addition to cyclic enones with chiral bifunctional Ru amido catalysts",

abstract = "A practical asymmetric C-C bond formation to synthetically useful β-chiral cyclic ketones (>99% ee) using bifunctional chiral amido Ru catalysts under an S/C = 1000, the highest ratio achieved so far in the literature for this class of reactions, is described. The catalytic reactivity decreases in the order of Ru(Msdpen)(hmb) > Ru(Pfbsdpen)(hmb) > Ru(Tsdpen)(hmb) > Ru(PMsdpen)(hmb), where Ru(Pfbsdpen)(hmb) is a newly developed chiral bifunctional catalyst. Complex Ru(Msdpen)(hmb) was identified as the best in terms of reactivity and enantioface selectivity, whereas Ru(PMsdpen)(hmb) gave unsatisfactory results. An importance of the NH proton in the bifunctional catalyst for determining the enantioselectivity has been experimentally demonstrated. Valuable information for the reaction mechanism was accumulated.",

keywords = "Asymmetric Michael addition, Bifunctional catalyst, C-C bond formation, Cyclic enone, Ru catalyst",

author = "Dub, {Pavel A.} and Hui Wang and Masahito Watanabe and Gridnev, {Ilya D.} and Takao Ikariya",

note = "Funding Information: This work was financially supported by the Grant-in-Aid from the MEXT (Japan, No. 22225004 ), the G-COE Program, Grant-in-Aid for Scientific Research for JSPS Postdoctoral Fellows ( 10F00344 ). PAD thanks the JSPS for the Postdoctoral Research Fellowship. ",

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doi = "10.1016/j.tetlet.2012.04.100",

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AU - Dub, Pavel A.

AU - Wang, Hui

AU - Watanabe, Masahito

AU - Gridnev, Ilya D.

AU - Ikariya, Takao

N1 - Funding Information: This work was financially supported by the Grant-in-Aid from the MEXT (Japan, No. 22225004 ), the G-COE Program, Grant-in-Aid for Scientific Research for JSPS Postdoctoral Fellows ( 10F00344 ). PAD thanks the JSPS for the Postdoctoral Research Fellowship.

PY - 2012/7/4

Y1 - 2012/7/4

N2 - A practical asymmetric C-C bond formation to synthetically useful β-chiral cyclic ketones (>99% ee) using bifunctional chiral amido Ru catalysts under an S/C = 1000, the highest ratio achieved so far in the literature for this class of reactions, is described. The catalytic reactivity decreases in the order of Ru(Msdpen)(hmb) > Ru(Pfbsdpen)(hmb) > Ru(Tsdpen)(hmb) > Ru(PMsdpen)(hmb), where Ru(Pfbsdpen)(hmb) is a newly developed chiral bifunctional catalyst. Complex Ru(Msdpen)(hmb) was identified as the best in terms of reactivity and enantioface selectivity, whereas Ru(PMsdpen)(hmb) gave unsatisfactory results. An importance of the NH proton in the bifunctional catalyst for determining the enantioselectivity has been experimentally demonstrated. Valuable information for the reaction mechanism was accumulated.

AB - A practical asymmetric C-C bond formation to synthetically useful β-chiral cyclic ketones (>99% ee) using bifunctional chiral amido Ru catalysts under an S/C = 1000, the highest ratio achieved so far in the literature for this class of reactions, is described. The catalytic reactivity decreases in the order of Ru(Msdpen)(hmb) > Ru(Pfbsdpen)(hmb) > Ru(Tsdpen)(hmb) > Ru(PMsdpen)(hmb), where Ru(Pfbsdpen)(hmb) is a newly developed chiral bifunctional catalyst. Complex Ru(Msdpen)(hmb) was identified as the best in terms of reactivity and enantioface selectivity, whereas Ru(PMsdpen)(hmb) gave unsatisfactory results. An importance of the NH proton in the bifunctional catalyst for determining the enantioselectivity has been experimentally demonstrated. Valuable information for the reaction mechanism was accumulated.

KW - Asymmetric Michael addition

KW - Bifunctional catalyst

KW - C-C bond formation

KW - Cyclic enone

KW - Ru catalyst

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A practical asymmetric conjugate addition to cyclic enones with chiral bifunctional Ru amido catalysts

Abstract

Keywords

ASJC Scopus subject areas

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