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Asymmetric Reduction of Prochiral $alpha,eta$-Acetylenic Ketones With Potassium 9-0-(1,2 : 5,6-Di-O-isopropylidene-$alpha$-D-glucofuranosyl)-9-bortabicylco[3.3.1]nonane$^dag$
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  • Asymmetric Reduction of Prochiral $alpha,eta$-Acetylenic Ketones With Potassium 9-0-(1,2 : 5,6-Di-O-isopropylidene-$alpha$-D-glucofuranosyl)-9-bortabicylco[3.3.1]nonane$^dag$
저자명
Cho. Byung-Tae,Park. Won-Suh
간행물명
Bulletin of the Korean Chemical Society
권/호정보
1987년|8권 4호|pp.257-260 (4 pages)
발행정보
대한화학회
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정기간행물|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
서지반출

기타언어초록

The asymmetric reduction of representative prochiral ${alpha},{eta}$-acetylenic ketones with a new chiral borohydride reducing agent, potassium 9-0-(1,2: 5,6-Di-O-isopropylidene-${alpha}$ -D-glucofuranosyl)-9-boratabicyclo[3.3.1]nonane, 1, in THF at $-78^{circ}C$ was studied. Structurally different acetylenic ketones such as internal ${alpha},{eta}$-acetylenic ketones $RC {equiv} CCOCH_3$ and terminal ${alpha},{eta}$-acetylenic ketones $HC {equiv} CCOR$ were chosen. Thus, the reduction of internal ${alpha},{eta}$-acetylenic ketones yields the corresponding propargyl alcohols, such as 67% ee for 3-hexyn-2-one, 75% ee for 5-methyl-3-hexyn-2-one, 86% ee for 5,5-dimethyl-3-hexyn-2-one, 74% ee for 3-nonyn-2-one and 61% ee for 4-phenyl-3-butyn-2-one. Terminal ${alpha},{eta}$-acetylenic ketones, such as 3-butyn-2-one, 1-pentyn-3-one, 4-methyl-1-pentyn-3-one and 1-octyn-3-one, are reduced to the corresponding alcohols with 59% ee, 17% ee, 44% ee and 12% ee of optical induction respectively. With one exception (4-methyl-1-pentyn-3-one), all propargyl alcohols obtained are enriched in R-enantiomers.