Enantioselective 1,4-addition of Ar3Bi, [ArBF3]K, and ArSiF3 to enones catalyzed by a dicationic palladium(II)-chiraphos or - Dipamp complex

Takashi Nishikata; Yasunori Yamamoto; Ilya D. Gridnev; Norio Miyaura

doi:10.1021/om050678t

Enantioselective 1,4-addition of Ar₃Bi, [ArBF₃]K, and ArSiF₃ to enones catalyzed by a dicationic palladium(II)-chiraphos or - Dipamp complex

Takashi Nishikata, Yasunori Yamamoto, Ilya D. Gridnev, Norio Miyaura

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

105 Citations (Scopus)

Abstract

Chiral complexes of [Pd(S,S-chiraphos)(PhCN)₂](SbF ₆)₂ (2b) and [Pd(S,S-dipamp)(PhCN)₂]-(SbF ₆)₂ (2c) catalyzed the highly enantioselective 1,4-additions of Ar₃Bi, [ArBF₃]K, and ArSiF₃ to cyclic and acyclic enones in aqueous methanol. The complexes catalyzed the reactions of Ar₃Bi and ArSiF₃ at 0-5°C in the presence of Cu(BF₄) or ZnF₂, whereas they smoothly prompted the addition of [ArBF₃]K at -15°C without further activation of the catalysts. The highest enantioselectivities giving β-aryl ketones up to 99% ee were attained when using 2b for 2-cyclopentenone and acyclic (E)-enones, whereas 2c resulted in the best selectivities for 2-cyclohexenone and 2-cycloheptenone (89-96% ee). The effects on enantioselection of chiral ligands and substituents on α,β-unsaturated ketones are discussed on the basis of X-ray structures of 2b and 2c as well as DFT computational studies on mechanistic aspects of the catalytic cycle.

Original language	English
Pages (from-to)	5025-5032
Number of pages	8
Journal	Organometallics
Volume	24
Issue number	21
DOIs	https://doi.org/10.1021/om050678t
Publication status	Published - 2005 Oct 10
Externally published	Yes

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Enantioselective 1,4-addition of Ar3Bi, [ArBF3]K, and ArSiF3 to enones catalyzed by a dicationic palladium(II)-chiraphos or - Dipamp complex",

abstract = "Chiral complexes of [Pd(S,S-chiraphos)(PhCN)2](SbF 6)2 (2b) and [Pd(S,S-dipamp)(PhCN)2]-(SbF 6)2 (2c) catalyzed the highly enantioselective 1,4-additions of Ar3Bi, [ArBF3]K, and ArSiF3 to cyclic and acyclic enones in aqueous methanol. The complexes catalyzed the reactions of Ar3Bi and ArSiF3 at 0-5°C in the presence of Cu(BF4) or ZnF2, whereas they smoothly prompted the addition of [ArBF3]K at -15°C without further activation of the catalysts. The highest enantioselectivities giving β-aryl ketones up to 99% ee were attained when using 2b for 2-cyclopentenone and acyclic (E)-enones, whereas 2c resulted in the best selectivities for 2-cyclohexenone and 2-cycloheptenone (89-96% ee). The effects on enantioselection of chiral ligands and substituents on α,β-unsaturated ketones are discussed on the basis of X-ray structures of 2b and 2c as well as DFT computational studies on mechanistic aspects of the catalytic cycle.",

author = "Takashi Nishikata and Yasunori Yamamoto and Gridnev, {Ilya D.} and Norio Miyaura",

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T1 - Enantioselective 1,4-addition of Ar3Bi, [ArBF3]K, and ArSiF3 to enones catalyzed by a dicationic palladium(II)-chiraphos or - Dipamp complex

AU - Nishikata, Takashi

AU - Yamamoto, Yasunori

AU - Gridnev, Ilya D.

AU - Miyaura, Norio

PY - 2005/10/10

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N2 - Chiral complexes of [Pd(S,S-chiraphos)(PhCN)2](SbF 6)2 (2b) and [Pd(S,S-dipamp)(PhCN)2]-(SbF 6)2 (2c) catalyzed the highly enantioselective 1,4-additions of Ar3Bi, [ArBF3]K, and ArSiF3 to cyclic and acyclic enones in aqueous methanol. The complexes catalyzed the reactions of Ar3Bi and ArSiF3 at 0-5°C in the presence of Cu(BF4) or ZnF2, whereas they smoothly prompted the addition of [ArBF3]K at -15°C without further activation of the catalysts. The highest enantioselectivities giving β-aryl ketones up to 99% ee were attained when using 2b for 2-cyclopentenone and acyclic (E)-enones, whereas 2c resulted in the best selectivities for 2-cyclohexenone and 2-cycloheptenone (89-96% ee). The effects on enantioselection of chiral ligands and substituents on α,β-unsaturated ketones are discussed on the basis of X-ray structures of 2b and 2c as well as DFT computational studies on mechanistic aspects of the catalytic cycle.

AB - Chiral complexes of [Pd(S,S-chiraphos)(PhCN)2](SbF 6)2 (2b) and [Pd(S,S-dipamp)(PhCN)2]-(SbF 6)2 (2c) catalyzed the highly enantioselective 1,4-additions of Ar3Bi, [ArBF3]K, and ArSiF3 to cyclic and acyclic enones in aqueous methanol. The complexes catalyzed the reactions of Ar3Bi and ArSiF3 at 0-5°C in the presence of Cu(BF4) or ZnF2, whereas they smoothly prompted the addition of [ArBF3]K at -15°C without further activation of the catalysts. The highest enantioselectivities giving β-aryl ketones up to 99% ee were attained when using 2b for 2-cyclopentenone and acyclic (E)-enones, whereas 2c resulted in the best selectivities for 2-cyclohexenone and 2-cycloheptenone (89-96% ee). The effects on enantioselection of chiral ligands and substituents on α,β-unsaturated ketones are discussed on the basis of X-ray structures of 2b and 2c as well as DFT computational studies on mechanistic aspects of the catalytic cycle.

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Enantioselective 1,4-addition of Ar₃Bi, [ArBF₃]K, and ArSiF₃ to enones catalyzed by a dicationic palladium(II)-chiraphos or - Dipamp complex

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