Chiral γ-(tetrahydropyranyloxy)allylstannane: a new chiral reagent for the asymmetric synthesis of syn 1,2-diols

Isao Kadota, Katsumi Kobayashi, Hiroshi Okano, Naoki Asao, Yoshinori Yamamoto

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

(2R,3S)-3-Allyloxy-3,4,5,6-tetrahydro-2H-pyran-2-methanol was prepared in high yield from tri-O-acetyl-d-glucal, an easily available and cheap chiral source. The hydroxyl group was protected as the t-butyldiphenylsilyl ether, and the allyl group was converted to the corresponding allyl stannane via formation of allyl carbanion and subsequent trapping with tributylstannyl chloride. The γ-alkoxy allyl stannane 1 bearing the (2R,3S)-2-[(t-butyldiphenylsilyloxy)methyl]-3,4,5,6-tetrahydro-2H-pyran-3-yloxy auxiliary at the allyl terminus was prepared by this procedure. The reaction of 1 with aldehydes in the presence of AlCl3 · OEt2 or AlCl3 gave the corresponding syn adducts 2 with high diastereoselectivities; the ratio of syn/anti > 97:3. The diastereomeric excess of the syn adducts 2, that is, the ratio 2/(2 + the (S,S) isomer of 2), varied from 85 to 94%. Removal of the protecting group of 2 gave the (R,R) diols 3. The high diastereo- and enantioselectivity in the formation of the (R,R) isomer is accounted for by an anti s′E transition state 18.

Original languageEnglish
Pages (from-to)615-623
Number of pages9
JournalBulletin de la Societe Chimique de France
Volume132
Issue number5-6
Publication statusPublished - 1995
Externally publishedYes

Fingerprint

Pyrans
Isomers
Bearings (structural)
Enantioselectivity
Aldehydes
Hydroxyl Radical
Ether
Methanol
Chlorides
aluminum chloride
stannane
alkoxyl radical
d-glucal

Keywords

  • 2-diol / Lewis acid / allylstannane-aldehyde condensation / γ-(tetrahydropyranyloxy)allylstannane / anti s′
  • allylstannane / γ-alkoxyallylstannane / asymmetric synthesis / syn-1

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Chiral γ-(tetrahydropyranyloxy)allylstannane : a new chiral reagent for the asymmetric synthesis of syn 1,2-diols. / Kadota, Isao; Kobayashi, Katsumi; Okano, Hiroshi; Asao, Naoki; Yamamoto, Yoshinori.

In: Bulletin de la Societe Chimique de France, Vol. 132, No. 5-6, 1995, p. 615-623.

Research output: Contribution to journalArticle

Kadota, Isao ; Kobayashi, Katsumi ; Okano, Hiroshi ; Asao, Naoki ; Yamamoto, Yoshinori. / Chiral γ-(tetrahydropyranyloxy)allylstannane : a new chiral reagent for the asymmetric synthesis of syn 1,2-diols. In: Bulletin de la Societe Chimique de France. 1995 ; Vol. 132, No. 5-6. pp. 615-623.
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T1 - Chiral γ-(tetrahydropyranyloxy)allylstannane

T2 - a new chiral reagent for the asymmetric synthesis of syn 1,2-diols

AU - Kadota, Isao

AU - Kobayashi, Katsumi

AU - Okano, Hiroshi

AU - Asao, Naoki

AU - Yamamoto, Yoshinori

PY - 1995

Y1 - 1995

N2 - (2R,3S)-3-Allyloxy-3,4,5,6-tetrahydro-2H-pyran-2-methanol was prepared in high yield from tri-O-acetyl-d-glucal, an easily available and cheap chiral source. The hydroxyl group was protected as the t-butyldiphenylsilyl ether, and the allyl group was converted to the corresponding allyl stannane via formation of allyl carbanion and subsequent trapping with tributylstannyl chloride. The γ-alkoxy allyl stannane 1 bearing the (2R,3S)-2-[(t-butyldiphenylsilyloxy)methyl]-3,4,5,6-tetrahydro-2H-pyran-3-yloxy auxiliary at the allyl terminus was prepared by this procedure. The reaction of 1 with aldehydes in the presence of AlCl3 · OEt2 or AlCl3 gave the corresponding syn adducts 2 with high diastereoselectivities; the ratio of syn/anti > 97:3. The diastereomeric excess of the syn adducts 2, that is, the ratio 2/(2 + the (S,S) isomer of 2), varied from 85 to 94%. Removal of the protecting group of 2 gave the (R,R) diols 3. The high diastereo- and enantioselectivity in the formation of the (R,R) isomer is accounted for by an anti s′E transition state 18.

AB - (2R,3S)-3-Allyloxy-3,4,5,6-tetrahydro-2H-pyran-2-methanol was prepared in high yield from tri-O-acetyl-d-glucal, an easily available and cheap chiral source. The hydroxyl group was protected as the t-butyldiphenylsilyl ether, and the allyl group was converted to the corresponding allyl stannane via formation of allyl carbanion and subsequent trapping with tributylstannyl chloride. The γ-alkoxy allyl stannane 1 bearing the (2R,3S)-2-[(t-butyldiphenylsilyloxy)methyl]-3,4,5,6-tetrahydro-2H-pyran-3-yloxy auxiliary at the allyl terminus was prepared by this procedure. The reaction of 1 with aldehydes in the presence of AlCl3 · OEt2 or AlCl3 gave the corresponding syn adducts 2 with high diastereoselectivities; the ratio of syn/anti > 97:3. The diastereomeric excess of the syn adducts 2, that is, the ratio 2/(2 + the (S,S) isomer of 2), varied from 85 to 94%. Removal of the protecting group of 2 gave the (R,R) diols 3. The high diastereo- and enantioselectivity in the formation of the (R,R) isomer is accounted for by an anti s′E transition state 18.

KW - 2-diol / Lewis acid / allylstannane-aldehyde condensation / γ-(tetrahydropyranyloxy)allylstannane / anti s′

KW - allylstannane / γ-alkoxyallylstannane / asymmetric synthesis / syn-1

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