Concise enantioselective synthesis of δ,δ-disubstituted δ-valerolactones

Akira Saito; Naoya Kumagai; Masakatsu Shibasaki

doi:10.1016/j.tetlet.2014.04.006

Concise enantioselective synthesis of δ,δ-disubstituted δ-valerolactones

Akira Saito, Naoya Kumagai, Masakatsu Shibasaki

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

11 Citations (Scopus)

Abstract

Efficient access to enantioenriched δ,δ-disubstituted δ-valerolactones is described. A soft Lewis acid/hard Brønsted base cooperative catalyst allowed for direct catalytic asymmetric γ-addition of allyl cyanide to ketones, producing tertiary homoallylic alcohols with a Z-configured α,β-unsaturated nitrile. Electrophilic activation of the nitrile functionality triggered 6-exo-dig cyclization, and subsequent N-acylation gave rise to the δ-valerolactone skeleton via CN bond cleavage.

Original language	English
Pages (from-to)	3167-3171
Number of pages	5
Journal	Tetrahedron Letters
Volume	55
Issue number	20
DOIs	https://doi.org/10.1016/j.tetlet.2014.04.006
Publication status	Published - 2014 May 14
Externally published	Yes

Keywords

Cyclization
Nitrile
Silver
Valerolactone

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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10.1016/j.tetlet.2014.04.006

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title = "Concise enantioselective synthesis of δ,δ-disubstituted δ-valerolactones",

abstract = "Efficient access to enantioenriched δ,δ-disubstituted δ-valerolactones is described. A soft Lewis acid/hard Br{\o}nsted base cooperative catalyst allowed for direct catalytic asymmetric γ-addition of allyl cyanide to ketones, producing tertiary homoallylic alcohols with a Z-configured α,β-unsaturated nitrile. Electrophilic activation of the nitrile functionality triggered 6-exo-dig cyclization, and subsequent N-acylation gave rise to the δ-valerolactone skeleton via CN bond cleavage.",

keywords = "Cyclization, Nitrile, Silver, Valerolactone",

author = "Akira Saito and Naoya Kumagai and Masakatsu Shibasaki",

note = "Funding Information: This work was financially supported by JST , ACT-C , and JSPS KAKENHI Grant Number 25713002 . We thank Dr. Yasunari Otsuka at the Institute of Microbial Chemistry for initial experiments at the early stage of this study. ",

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doi = "10.1016/j.tetlet.2014.04.006",

language = "English",

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T1 - Concise enantioselective synthesis of δ,δ-disubstituted δ-valerolactones

AU - Saito, Akira

AU - Kumagai, Naoya

AU - Shibasaki, Masakatsu

N1 - Funding Information: This work was financially supported by JST , ACT-C , and JSPS KAKENHI Grant Number 25713002 . We thank Dr. Yasunari Otsuka at the Institute of Microbial Chemistry for initial experiments at the early stage of this study.

PY - 2014/5/14

Y1 - 2014/5/14

N2 - Efficient access to enantioenriched δ,δ-disubstituted δ-valerolactones is described. A soft Lewis acid/hard Brønsted base cooperative catalyst allowed for direct catalytic asymmetric γ-addition of allyl cyanide to ketones, producing tertiary homoallylic alcohols with a Z-configured α,β-unsaturated nitrile. Electrophilic activation of the nitrile functionality triggered 6-exo-dig cyclization, and subsequent N-acylation gave rise to the δ-valerolactone skeleton via CN bond cleavage.

AB - Efficient access to enantioenriched δ,δ-disubstituted δ-valerolactones is described. A soft Lewis acid/hard Brønsted base cooperative catalyst allowed for direct catalytic asymmetric γ-addition of allyl cyanide to ketones, producing tertiary homoallylic alcohols with a Z-configured α,β-unsaturated nitrile. Electrophilic activation of the nitrile functionality triggered 6-exo-dig cyclization, and subsequent N-acylation gave rise to the δ-valerolactone skeleton via CN bond cleavage.

KW - Cyclization

KW - Nitrile

KW - Silver

KW - Valerolactone

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DO - 10.1016/j.tetlet.2014.04.006

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JO - Tetrahedron Letters

JF - Tetrahedron Letters

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Concise enantioselective synthesis of δ,δ-disubstituted δ-valerolactones

Abstract

Keywords

ASJC Scopus subject areas

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