Asymmetric hydrosilylation of ketones using trans-chelating chiral peralkylbisphosphine ligands bearing primary alkyl substituents on phosphorus atoms

Ryoichi Kuwano, Masaya Sawamura, Junya Shirai, Masatoshi Takahashi, Yoshihiko Ito

Research output: Contribution to journalArticle

53 Citations (Scopus)

Abstract

Asymmetric hydrosilylation of simple ketones with diphenylsilane proceeded at -40 °C in the presence of a rhodium complex (0.001 - 0.01 molar amount) coordinated with a trans-chelating chiral bisphosphine ligand bearing linear alkyl substituents on the phosphorus atoms, (R,R)-(S,S)-Et-, Pr-, or BuTRAP, giving the corresponding optically active (S)- secondary alcohols with up to 97% ee. The asymmetric hydrosilylation using TRAP ligands with bulkier P-substituents resulted in much lower enantioselectivities. The EtTRAP-rhodium catalyst was also effective for asymmetric hydrosilylation of keto esters with a coordination site for a rhodium atom (up to 98% ee). Optically active symmetrical diols were obtained with up to 99% ee from the corresponding diketones via the asymmetric reduction using 2.5 molar amounts of diphenylsilane.

Original languageEnglish
Pages (from-to)485-496
Number of pages12
JournalBulletin of the Chemical Society of Japan
Volume73
Issue number2
DOIs
Publication statusPublished - Feb 1 2000
Externally publishedYes

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Bearings (structural)
Hydrosilylation
Rhodium
Chelation
Ketones
Phosphorus
Ligands
Atoms
Enantioselectivity
Esters
Alcohols
Catalysts

All Science Journal Classification (ASJC) codes

  • Chemistry(all)

Cite this

Asymmetric hydrosilylation of ketones using trans-chelating chiral peralkylbisphosphine ligands bearing primary alkyl substituents on phosphorus atoms. / Kuwano, Ryoichi; Sawamura, Masaya; Shirai, Junya; Takahashi, Masatoshi; Ito, Yoshihiko.

In: Bulletin of the Chemical Society of Japan, Vol. 73, No. 2, 01.02.2000, p. 485-496.

Research output: Contribution to journalArticle

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