Chiral and stereoselective total synthesis of novel immunosuppressant FR65814 from D-glucose

Seiji Amano; Noriko Ogawa; Masami Ohtsuka; Noritaka Chida

doi:10.1016/S0040-4020(99)00004-6

Chiral and stereoselective total synthesis of novel immunosuppressant FR65814 from D-glucose

Seiji Amano, Noriko Ogawa, Masami Ohtsuka, Noritaka Chida

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

48 Citations (Scopus)

Abstract

The chiral synthesis of the immunosuppressive sesquiterpene, FR65814 1 is described. The cyclohexane ring in 1 was prepared in an optically active form from D-glucose using Ferrier's carbocyclization reaction, and the carbon side-chain in 1 was stereoselectively introduced via chirality transfer by way of Claisen rearrangement of the cyclohexenol derivative, followed by Pd- catalyzed Stille coupling. The bis-epoxide function was stereoselectively constructed by sulfur ylide chemistry and vanadium catalyzed epoxidation of a homoallyl alcohol derivative. This first total synthesis fully confirmed the proposed absolute structure of FR65814.

Original language	English
Pages (from-to)	2205-2224
Number of pages	20
Journal	Tetrahedron
Volume	55
Issue number	8
DOIs	https://doi.org/10.1016/S0040-4020(99)00004-6
Publication status	Published - 1999 Feb 19
Externally published	Yes

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/S0040-4020(99)00004-6

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title = "Chiral and stereoselective total synthesis of novel immunosuppressant FR65814 from D-glucose",

abstract = "The chiral synthesis of the immunosuppressive sesquiterpene, FR65814 1 is described. The cyclohexane ring in 1 was prepared in an optically active form from D-glucose using Ferrier's carbocyclization reaction, and the carbon side-chain in 1 was stereoselectively introduced via chirality transfer by way of Claisen rearrangement of the cyclohexenol derivative, followed by Pd- catalyzed Stille coupling. The bis-epoxide function was stereoselectively constructed by sulfur ylide chemistry and vanadium catalyzed epoxidation of a homoallyl alcohol derivative. This first total synthesis fully confirmed the proposed absolute structure of FR65814.",

author = "Seiji Amano and Noriko Ogawa and Masami Ohtsuka and Noritaka Chida",

note = "Funding Information: We thank Fujisawa Pharmaceutical Co., Ltd., (Osaka, Japan) for providing us with natural FR65814. Financial support of the Grant-in Aid for Scientific Research on Priority Area from the Ministry of Education, Science, Sports and Culture, of Japanese Government is gratefully acknowledged.",

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doi = "10.1016/S0040-4020(99)00004-6",

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T1 - Chiral and stereoselective total synthesis of novel immunosuppressant FR65814 from D-glucose

AU - Amano, Seiji

AU - Ogawa, Noriko

AU - Ohtsuka, Masami

AU - Chida, Noritaka

N1 - Funding Information: We thank Fujisawa Pharmaceutical Co., Ltd., (Osaka, Japan) for providing us with natural FR65814. Financial support of the Grant-in Aid for Scientific Research on Priority Area from the Ministry of Education, Science, Sports and Culture, of Japanese Government is gratefully acknowledged.

PY - 1999/2/19

Y1 - 1999/2/19

N2 - The chiral synthesis of the immunosuppressive sesquiterpene, FR65814 1 is described. The cyclohexane ring in 1 was prepared in an optically active form from D-glucose using Ferrier's carbocyclization reaction, and the carbon side-chain in 1 was stereoselectively introduced via chirality transfer by way of Claisen rearrangement of the cyclohexenol derivative, followed by Pd- catalyzed Stille coupling. The bis-epoxide function was stereoselectively constructed by sulfur ylide chemistry and vanadium catalyzed epoxidation of a homoallyl alcohol derivative. This first total synthesis fully confirmed the proposed absolute structure of FR65814.

AB - The chiral synthesis of the immunosuppressive sesquiterpene, FR65814 1 is described. The cyclohexane ring in 1 was prepared in an optically active form from D-glucose using Ferrier's carbocyclization reaction, and the carbon side-chain in 1 was stereoselectively introduced via chirality transfer by way of Claisen rearrangement of the cyclohexenol derivative, followed by Pd- catalyzed Stille coupling. The bis-epoxide function was stereoselectively constructed by sulfur ylide chemistry and vanadium catalyzed epoxidation of a homoallyl alcohol derivative. This first total synthesis fully confirmed the proposed absolute structure of FR65814.

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DO - 10.1016/S0040-4020(99)00004-6

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JO - Tetrahedron

JF - Tetrahedron

IS - 8

ER -

Chiral and stereoselective total synthesis of novel immunosuppressant FR65814 from D-glucose

Abstract

ASJC Scopus subject areas

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