Rhodium-catalyzed reductive cyclization of 1,6-enynes and stereoselective synthesis of the putative structure of lucentamycin A and its stereoisomers

Young Jin Ham; Hana Yu; Nam Doo Kim; Jung Mi Hah; Khalid B. Selim; Hwan Geun Choi; Taebo Sim

doi:10.1016/j.tet.2011.12.075

Rhodium-catalyzed reductive cyclization of 1,6-enynes and stereoselective synthesis of the putative structure of lucentamycin A and its stereoisomers

Young Jin Ham, Hana Yu, Nam Doo Kim, Jung Mi Hah, Khalid B. Selim, Hwan Geun Choi, Taebo Sim

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

15 Citations (Scopus)

Abstract

A Rh-catalyzed diastereoselective reductive cyclization, mediated by hydrogen, of optically active 1,6-enynes using chiral BINAP was successfully applied to the total synthesis of four stereoisomers of the proposed structure of lucentamycin A. In order to synthesize two of these four stereoisomers, we successfully constructed chiral proline derivatives bearing cis-carbon substituents at C2 and C3 positions based on Krische's methodology, which has very rarely been reported. Anti-proliferative activities on HCT-116 cell line and NMR data of these four stereoisomers were compared with those of naturally occurring lucentamycine A. The results show that the proposed structure of lucentamycin A needs revision.

Original language	English
Pages (from-to)	1918-1925
Number of pages	8
Journal	Tetrahedron
Volume	68
Issue number	7
DOIs	https://doi.org/10.1016/j.tet.2011.12.075
Publication status	Published - 2012 Feb 18

Bibliographical note

Funding Information:
This research was supported by Korea Institute of Science and Technology (Grant: 2E22250 ) and a grant ( 2011-0028676 ) from the creative/challenging research program of National Research Foundation of Korea funded by the Ministry of Education, Science and Technology , Republic of Korea.

Keywords

1,6-Enynes
Lucentamycin A
Natural product
Reductive cyclization
Structure revision

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tet.2011.12.075

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title = "Rhodium-catalyzed reductive cyclization of 1,6-enynes and stereoselective synthesis of the putative structure of lucentamycin A and its stereoisomers",

abstract = "A Rh-catalyzed diastereoselective reductive cyclization, mediated by hydrogen, of optically active 1,6-enynes using chiral BINAP was successfully applied to the total synthesis of four stereoisomers of the proposed structure of lucentamycin A. In order to synthesize two of these four stereoisomers, we successfully constructed chiral proline derivatives bearing cis-carbon substituents at C2 and C3 positions based on Krische's methodology, which has very rarely been reported. Anti-proliferative activities on HCT-116 cell line and NMR data of these four stereoisomers were compared with those of naturally occurring lucentamycine A. The results show that the proposed structure of lucentamycin A needs revision.",

keywords = "1,6-Enynes, Lucentamycin A, Natural product, Reductive cyclization, Structure revision",

author = "Ham, {Young Jin} and Hana Yu and Kim, {Nam Doo} and Hah, {Jung Mi} and Selim, {Khalid B.} and Choi, {Hwan Geun} and Taebo Sim",

note = "Funding Information: This research was supported by Korea Institute of Science and Technology (Grant: 2E22250 ) and a grant ( 2011-0028676 ) from the creative/challenging research program of National Research Foundation of Korea funded by the Ministry of Education, Science and Technology , Republic of Korea.",

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T1 - Rhodium-catalyzed reductive cyclization of 1,6-enynes and stereoselective synthesis of the putative structure of lucentamycin A and its stereoisomers

AU - Ham, Young Jin

AU - Yu, Hana

AU - Kim, Nam Doo

AU - Hah, Jung Mi

AU - Selim, Khalid B.

AU - Choi, Hwan Geun

AU - Sim, Taebo

N1 - Funding Information: This research was supported by Korea Institute of Science and Technology (Grant: 2E22250 ) and a grant ( 2011-0028676 ) from the creative/challenging research program of National Research Foundation of Korea funded by the Ministry of Education, Science and Technology , Republic of Korea.

PY - 2012/2/18

Y1 - 2012/2/18

N2 - A Rh-catalyzed diastereoselective reductive cyclization, mediated by hydrogen, of optically active 1,6-enynes using chiral BINAP was successfully applied to the total synthesis of four stereoisomers of the proposed structure of lucentamycin A. In order to synthesize two of these four stereoisomers, we successfully constructed chiral proline derivatives bearing cis-carbon substituents at C2 and C3 positions based on Krische's methodology, which has very rarely been reported. Anti-proliferative activities on HCT-116 cell line and NMR data of these four stereoisomers were compared with those of naturally occurring lucentamycine A. The results show that the proposed structure of lucentamycin A needs revision.

AB - A Rh-catalyzed diastereoselective reductive cyclization, mediated by hydrogen, of optically active 1,6-enynes using chiral BINAP was successfully applied to the total synthesis of four stereoisomers of the proposed structure of lucentamycin A. In order to synthesize two of these four stereoisomers, we successfully constructed chiral proline derivatives bearing cis-carbon substituents at C2 and C3 positions based on Krische's methodology, which has very rarely been reported. Anti-proliferative activities on HCT-116 cell line and NMR data of these four stereoisomers were compared with those of naturally occurring lucentamycine A. The results show that the proposed structure of lucentamycin A needs revision.

KW - 1,6-Enynes

KW - Lucentamycin A

KW - Natural product

KW - Reductive cyclization

KW - Structure revision

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DO - 10.1016/j.tet.2011.12.075

M3 - Article

AN - SCOPUS:84856402549

SN - 0040-4020

VL - 68

SP - 1918

EP - 1925

JO - Tetrahedron

JF - Tetrahedron

IS - 7

ER -

Rhodium-catalyzed reductive cyclization of 1,6-enynes and stereoselective synthesis of the putative structure of lucentamycin A and its stereoisomers

Abstract

Bibliographical note

Keywords

ASJC Scopus subject areas

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