Enantioselective Formal C(sp2)−H Vinylation

Madhu Sudan Manna; Rahul Sarkar; Santanu Mukherjee

doi:10.1002/chem.201602253

Enantioselective Formal C(sp²)−H Vinylation

Madhu Sudan Manna, Rahul Sarkar, Santanu Mukherjee

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

24 Scopus citations

Abstract

An enantioselective formal C(sp²)−H vinylation of prochiral 2,2-disubstituted cyclopentene-1,3-dione is presented. This vinylative desymmetrization is realized by using a two-step procedure that consists of a catalytic enantioselective vinylogous Michael addition of deconjugated butenolides to cyclopentene-1,3-dione and a base-mediated decarboxylation. The overall process utilizes deconjugated butenolides as the source of the highly substituted vinyl unit. Five-membered carbocycles containing a remote all-carbon quaternary stereogenic center are obtained in good yields and with good to high enantioselectivities.

Original language	English (US)
Pages (from-to)	14912-14919
Number of pages	8
Journal	Chemistry - A European Journal
Volume	22
Issue number	42
DOIs	https://doi.org/10.1002/chem.201602253
State	Published - Oct 10 2016
Externally published	Yes

Keywords

C−H functionalization
decarboxylation
desymmetrization
lactones
vinylation

ASJC Scopus subject areas

Catalysis
Organic Chemistry

Access to Document

10.1002/chem.201602253

Cite this

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title = "Enantioselective Formal C(sp2)−H Vinylation",

abstract = "An enantioselective formal C(sp2)−H vinylation of prochiral 2,2-disubstituted cyclopentene-1,3-dione is presented. This vinylative desymmetrization is realized by using a two-step procedure that consists of a catalytic enantioselective vinylogous Michael addition of deconjugated butenolides to cyclopentene-1,3-dione and a base-mediated decarboxylation. The overall process utilizes deconjugated butenolides as the source of the highly substituted vinyl unit. Five-membered carbocycles containing a remote all-carbon quaternary stereogenic center are obtained in good yields and with good to high enantioselectivities.",

keywords = "C−H functionalization, decarboxylation, desymmetrization, lactones, vinylation",

author = "Manna, {Madhu Sudan} and Rahul Sarkar and Santanu Mukherjee",

note = "Funding Information: Financial support from SERB (grant no. SB/S1/OC-63/2013), CSIR (grant no. 02(0207)/14/EMR-II), and DAE-BRNS (grant no. 2013/37C/56/BRNS/2440) is gratefully acknowledged. M.S.M. thanks CSIR for a doctoral fellowship. We thank Mr. Amar A. Hosamani and Mr. Pavan M. S. (SSCU, IISc, Bangalore) for their help with the X-ray structure analysis. Publisher Copyright: {\textcopyright} 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2016",

month = oct,

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doi = "10.1002/chem.201602253",

language = "English (US)",

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journal = "Chemistry - A European Journal",

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AU - Manna, Madhu Sudan

AU - Sarkar, Rahul

AU - Mukherjee, Santanu

N1 - Funding Information: Financial support from SERB (grant no. SB/S1/OC-63/2013), CSIR (grant no. 02(0207)/14/EMR-II), and DAE-BRNS (grant no. 2013/37C/56/BRNS/2440) is gratefully acknowledged. M.S.M. thanks CSIR for a doctoral fellowship. We thank Mr. Amar A. Hosamani and Mr. Pavan M. S. (SSCU, IISc, Bangalore) for their help with the X-ray structure analysis. Publisher Copyright: © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2016/10/10

Y1 - 2016/10/10

N2 - An enantioselective formal C(sp2)−H vinylation of prochiral 2,2-disubstituted cyclopentene-1,3-dione is presented. This vinylative desymmetrization is realized by using a two-step procedure that consists of a catalytic enantioselective vinylogous Michael addition of deconjugated butenolides to cyclopentene-1,3-dione and a base-mediated decarboxylation. The overall process utilizes deconjugated butenolides as the source of the highly substituted vinyl unit. Five-membered carbocycles containing a remote all-carbon quaternary stereogenic center are obtained in good yields and with good to high enantioselectivities.

AB - An enantioselective formal C(sp2)−H vinylation of prochiral 2,2-disubstituted cyclopentene-1,3-dione is presented. This vinylative desymmetrization is realized by using a two-step procedure that consists of a catalytic enantioselective vinylogous Michael addition of deconjugated butenolides to cyclopentene-1,3-dione and a base-mediated decarboxylation. The overall process utilizes deconjugated butenolides as the source of the highly substituted vinyl unit. Five-membered carbocycles containing a remote all-carbon quaternary stereogenic center are obtained in good yields and with good to high enantioselectivities.

KW - C−H functionalization

KW - decarboxylation

KW - desymmetrization

KW - lactones

KW - vinylation

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