Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols Using Palladium and a Chiral Phosphoric Acid

Tomoya Miura; Junki Nakahashi; Masahiro Murakami

doi:10.1002/anie.201702611

Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols Using Palladium and a Chiral Phosphoric Acid

Tomoya Miura, Junki Nakahashi, Masahiro Murakami

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

59 Citations (Scopus)

Abstract

(E)-δ-Boryl-substituted anti-homoallylic alcohols are synthesized in a highly diastereo- and enantioselective manner from 1,1-di(boryl)alk-3-enes and aldehydes. Mechanistically, the reaction consists of 1) palladium-catalyzed double-bond transposition of the 1,1-di(boryl)alk-3-enes to 1,1-di(boryl)alk-2-enes, 2) chiral phosphoric acid catalyzed allylation of aldehydes, and 3) palladium-catalyzed geometrical isomerization from the Z to E isomer. As a result, the configurations of two chiral centers and one double bond are all controlled with high selectivity in a single reaction vessel.

Original language	English
Pages (from-to)	6989-6993
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	56
Issue number	24
DOIs	https://doi.org/10.1002/anie.201702611
Publication status	Published - Jun 6 2017
Externally published	Yes

Keywords

allylation
asymmetric synthesis
homoallylic compounds
organocatalysis
palladium

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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10.1002/anie.201702611

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title = "Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols Using Palladium and a Chiral Phosphoric Acid",

abstract = "(E)-δ-Boryl-substituted anti-homoallylic alcohols are synthesized in a highly diastereo- and enantioselective manner from 1,1-di(boryl)alk-3-enes and aldehydes. Mechanistically, the reaction consists of 1) palladium-catalyzed double-bond transposition of the 1,1-di(boryl)alk-3-enes to 1,1-di(boryl)alk-2-enes, 2) chiral phosphoric acid catalyzed allylation of aldehydes, and 3) palladium-catalyzed geometrical isomerization from the Z to E isomer. As a result, the configurations of two chiral centers and one double bond are all controlled with high selectivity in a single reaction vessel.",

keywords = "allylation, asymmetric synthesis, homoallylic compounds, organocatalysis, palladium",

author = "Tomoya Miura and Junki Nakahashi and Masahiro Murakami",

note = "Funding Information: This work was supported by Grants-in-Aid for Scientific Research (S) (15H05756) and (C) (16K05694) from MEXT. Publisher Copyright: {\textcopyright} 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2017",

month = jun,

day = "6",

doi = "10.1002/anie.201702611",

language = "English",

volume = "56",

pages = "6989--6993",

journal = "Angewandte Chemie - International Edition",

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T1 - Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols Using Palladium and a Chiral Phosphoric Acid

AU - Miura, Tomoya

AU - Nakahashi, Junki

AU - Murakami, Masahiro

N1 - Funding Information: This work was supported by Grants-in-Aid for Scientific Research (S) (15H05756) and (C) (16K05694) from MEXT. Publisher Copyright: © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2017/6/6

Y1 - 2017/6/6

N2 - (E)-δ-Boryl-substituted anti-homoallylic alcohols are synthesized in a highly diastereo- and enantioselective manner from 1,1-di(boryl)alk-3-enes and aldehydes. Mechanistically, the reaction consists of 1) palladium-catalyzed double-bond transposition of the 1,1-di(boryl)alk-3-enes to 1,1-di(boryl)alk-2-enes, 2) chiral phosphoric acid catalyzed allylation of aldehydes, and 3) palladium-catalyzed geometrical isomerization from the Z to E isomer. As a result, the configurations of two chiral centers and one double bond are all controlled with high selectivity in a single reaction vessel.

AB - (E)-δ-Boryl-substituted anti-homoallylic alcohols are synthesized in a highly diastereo- and enantioselective manner from 1,1-di(boryl)alk-3-enes and aldehydes. Mechanistically, the reaction consists of 1) palladium-catalyzed double-bond transposition of the 1,1-di(boryl)alk-3-enes to 1,1-di(boryl)alk-2-enes, 2) chiral phosphoric acid catalyzed allylation of aldehydes, and 3) palladium-catalyzed geometrical isomerization from the Z to E isomer. As a result, the configurations of two chiral centers and one double bond are all controlled with high selectivity in a single reaction vessel.

KW - allylation

KW - asymmetric synthesis

KW - homoallylic compounds

KW - organocatalysis

KW - palladium

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DO - 10.1002/anie.201702611

M3 - Article

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VL - 56

SP - 6989

EP - 6993

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 24

ER -

Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols Using Palladium and a Chiral Phosphoric Acid

Abstract

Keywords

ASJC Scopus subject areas

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