A chiral cyclohex-2-enone carrying a hexofuranosyl substituent which directs highly stereoselective 1,4-conjugate additions

Takeshi Murata, Yumiko Yanagisawa, Makiko Aoyama, Hirona Tsushima, Kiichiro Totani, Shigeru Ohba, Kin Ichi Tadano

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The reaction of (Z)-3-deoxy-3-C-[(hydroxymethyl)methylene]-1,2:5,6-di- O-isopropylidene-α-D-ribo-hexofuranose, prepared from D-glucose, with 1,1- dimethoxycyclohexane in the presence of propanoic acid at 135°C, then at 200°C, provided two Claisen rearrangement products, namely (2R,3R,4S,5S)- 2,3-(isopropylidene)dioxy-5-[(1R)-1,2-(isopropylidene)dioxyethyl]-4-[(1S)- and (1R)-2-oxocyclohexyl]-4-vinyltetrahydrofuran in a ratio of 3.3:1. L- Selectride® reduction of the major product gave the corresponding (S)- cyclohexanol exclusively. In contrast, the Claisen rearrangement of the aforementioned allylic alcohol with 3,3-dimethoxycyclohexene proceeded with complete stereoselectivity to provide the corresponding 4-[(1S)-2- oxocyclohex-3-enyl]-4-vinyltetrahydrofuran exclusively. The 1,4-conjugate additions to the thus formed cyclohexenone derivative with dimethyl and divinylcuprates proceeded with complete π-facial selection to provide the 3- methylated and 3-vinylated cyclohexanone derivatives, both in high yields.

Original languageEnglish
Pages (from-to)4203-4217
Number of pages15
JournalTetrahedron Asymmetry
Volume9
Issue number23
DOIs
Publication statusPublished - 1998 Dec 11

Fingerprint

Derivatives
Stereoselectivity
products
Cyclohexanols
methylene
glucose
Glucose
alcohols
Alcohols
acids
Acids
propylene
selectride
propionic acid
allyl alcohol
cyclohexanone

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry
  • Materials Chemistry
  • Drug Discovery

Cite this

A chiral cyclohex-2-enone carrying a hexofuranosyl substituent which directs highly stereoselective 1,4-conjugate additions. / Murata, Takeshi; Yanagisawa, Yumiko; Aoyama, Makiko; Tsushima, Hirona; Totani, Kiichiro; Ohba, Shigeru; Tadano, Kin Ichi.

In: Tetrahedron Asymmetry, Vol. 9, No. 23, 11.12.1998, p. 4203-4217.

Research output: Contribution to journalArticle

Murata, Takeshi ; Yanagisawa, Yumiko ; Aoyama, Makiko ; Tsushima, Hirona ; Totani, Kiichiro ; Ohba, Shigeru ; Tadano, Kin Ichi. / A chiral cyclohex-2-enone carrying a hexofuranosyl substituent which directs highly stereoselective 1,4-conjugate additions. In: Tetrahedron Asymmetry. 1998 ; Vol. 9, No. 23. pp. 4203-4217.
@article{094bd75e9bce4bd58179040386445b86,
title = "A chiral cyclohex-2-enone carrying a hexofuranosyl substituent which directs highly stereoselective 1,4-conjugate additions",
abstract = "The reaction of (Z)-3-deoxy-3-C-[(hydroxymethyl)methylene]-1,2:5,6-di- O-isopropylidene-α-D-ribo-hexofuranose, prepared from D-glucose, with 1,1- dimethoxycyclohexane in the presence of propanoic acid at 135°C, then at 200°C, provided two Claisen rearrangement products, namely (2R,3R,4S,5S)- 2,3-(isopropylidene)dioxy-5-[(1R)-1,2-(isopropylidene)dioxyethyl]-4-[(1S)- and (1R)-2-oxocyclohexyl]-4-vinyltetrahydrofuran in a ratio of 3.3:1. L- Selectride{\circledR} reduction of the major product gave the corresponding (S)- cyclohexanol exclusively. In contrast, the Claisen rearrangement of the aforementioned allylic alcohol with 3,3-dimethoxycyclohexene proceeded with complete stereoselectivity to provide the corresponding 4-[(1S)-2- oxocyclohex-3-enyl]-4-vinyltetrahydrofuran exclusively. The 1,4-conjugate additions to the thus formed cyclohexenone derivative with dimethyl and divinylcuprates proceeded with complete π-facial selection to provide the 3- methylated and 3-vinylated cyclohexanone derivatives, both in high yields.",
author = "Takeshi Murata and Yumiko Yanagisawa and Makiko Aoyama and Hirona Tsushima and Kiichiro Totani and Shigeru Ohba and Tadano, {Kin Ichi}",
year = "1998",
month = "12",
day = "11",
doi = "10.1016/S0957-4166(98)00465-0",
language = "English",
volume = "9",
pages = "4203--4217",
journal = "Tetrahedron Asymmetry",
issn = "0957-4166",
publisher = "Elsevier Limited",
number = "23",

}

TY - JOUR

T1 - A chiral cyclohex-2-enone carrying a hexofuranosyl substituent which directs highly stereoselective 1,4-conjugate additions

AU - Murata, Takeshi

AU - Yanagisawa, Yumiko

AU - Aoyama, Makiko

AU - Tsushima, Hirona

AU - Totani, Kiichiro

AU - Ohba, Shigeru

AU - Tadano, Kin Ichi

PY - 1998/12/11

Y1 - 1998/12/11

N2 - The reaction of (Z)-3-deoxy-3-C-[(hydroxymethyl)methylene]-1,2:5,6-di- O-isopropylidene-α-D-ribo-hexofuranose, prepared from D-glucose, with 1,1- dimethoxycyclohexane in the presence of propanoic acid at 135°C, then at 200°C, provided two Claisen rearrangement products, namely (2R,3R,4S,5S)- 2,3-(isopropylidene)dioxy-5-[(1R)-1,2-(isopropylidene)dioxyethyl]-4-[(1S)- and (1R)-2-oxocyclohexyl]-4-vinyltetrahydrofuran in a ratio of 3.3:1. L- Selectride® reduction of the major product gave the corresponding (S)- cyclohexanol exclusively. In contrast, the Claisen rearrangement of the aforementioned allylic alcohol with 3,3-dimethoxycyclohexene proceeded with complete stereoselectivity to provide the corresponding 4-[(1S)-2- oxocyclohex-3-enyl]-4-vinyltetrahydrofuran exclusively. The 1,4-conjugate additions to the thus formed cyclohexenone derivative with dimethyl and divinylcuprates proceeded with complete π-facial selection to provide the 3- methylated and 3-vinylated cyclohexanone derivatives, both in high yields.

AB - The reaction of (Z)-3-deoxy-3-C-[(hydroxymethyl)methylene]-1,2:5,6-di- O-isopropylidene-α-D-ribo-hexofuranose, prepared from D-glucose, with 1,1- dimethoxycyclohexane in the presence of propanoic acid at 135°C, then at 200°C, provided two Claisen rearrangement products, namely (2R,3R,4S,5S)- 2,3-(isopropylidene)dioxy-5-[(1R)-1,2-(isopropylidene)dioxyethyl]-4-[(1S)- and (1R)-2-oxocyclohexyl]-4-vinyltetrahydrofuran in a ratio of 3.3:1. L- Selectride® reduction of the major product gave the corresponding (S)- cyclohexanol exclusively. In contrast, the Claisen rearrangement of the aforementioned allylic alcohol with 3,3-dimethoxycyclohexene proceeded with complete stereoselectivity to provide the corresponding 4-[(1S)-2- oxocyclohex-3-enyl]-4-vinyltetrahydrofuran exclusively. The 1,4-conjugate additions to the thus formed cyclohexenone derivative with dimethyl and divinylcuprates proceeded with complete π-facial selection to provide the 3- methylated and 3-vinylated cyclohexanone derivatives, both in high yields.

UR - http://www.scopus.com/inward/record.url?scp=0032509270&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0032509270&partnerID=8YFLogxK

U2 - 10.1016/S0957-4166(98)00465-0

DO - 10.1016/S0957-4166(98)00465-0

M3 - Article

VL - 9

SP - 4203

EP - 4217

JO - Tetrahedron Asymmetry

JF - Tetrahedron Asymmetry

SN - 0957-4166

IS - 23

ER -