Diastereo- and Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols in Two Steps from Terminal Alkynes

Tomoya Miura; Naoki Oku; Masahiro Murakami

doi:10.1002/anie.201908299

Diastereo- and Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols in Two Steps from Terminal Alkynes

Tomoya Miura, Naoki Oku, Masahiro Murakami

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

23 Citations (Scopus)

Abstract

We report the highly diastereo- and enantioselective preparation of (E)-δ-boryl-substituted anti-homoallylic alcohols in two steps from terminal alkynes. This method consists of a cobalt(II)-catalyzed 1,1-diboration reaction of terminal alkynes with B₂pin₂ and a palladium(I)-mediated asymmetric allylation reaction of the resulting 1,1-di(boryl)alk-1-enes with aldehydes in the presence of a chiral phosphoric acid. Propyne, which is produced as the byproduct during petroleum refining, could be used as the starting material to construct homoallylic alcohols that are otherwise difficult to synthesize with high stereocontrol.

Original language	English
Pages (from-to)	14620-14624
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	58
Issue number	41
DOIs	https://doi.org/10.1002/anie.201908299
Publication status	Published - Oct 7 2019
Externally published	Yes

Keywords

allylation
asymmetric catalysis
double-bond transposition
homoallylic compounds
palladium

ASJC Scopus subject areas

Catalysis
Chemistry(all)

Access to Document

10.1002/anie.201908299

Cite this

@article{0b43754b55b2428b9d19c119ad6f7e03,

title = "Diastereo- and Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols in Two Steps from Terminal Alkynes",

abstract = "We report the highly diastereo- and enantioselective preparation of (E)-δ-boryl-substituted anti-homoallylic alcohols in two steps from terminal alkynes. This method consists of a cobalt(II)-catalyzed 1,1-diboration reaction of terminal alkynes with B2pin2 and a palladium(I)-mediated asymmetric allylation reaction of the resulting 1,1-di(boryl)alk-1-enes with aldehydes in the presence of a chiral phosphoric acid. Propyne, which is produced as the byproduct during petroleum refining, could be used as the starting material to construct homoallylic alcohols that are otherwise difficult to synthesize with high stereocontrol.",

keywords = "allylation, asymmetric catalysis, double-bond transposition, homoallylic compounds, palladium",

author = "Tomoya Miura and Naoki Oku and Masahiro Murakami",

note = "Funding Information: This work was supported by MEXT [Grants‐in‐Aids for Scientific Research (S) (15H05756)] and ISHIZUE 2019 of Kyoto University Research Development Program. We thank Mr. J. Nakahashi (Kyoto Univ.) for his contribution at a preliminary stage. Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2019",

month = oct,

day = "7",

doi = "10.1002/anie.201908299",

language = "English",

volume = "58",

pages = "14620--14624",

journal = "Angewandte Chemie - International Edition",

issn = "1433-7851",

publisher = "John Wiley and Sons Ltd",

number = "41",

}

TY - JOUR

T1 - Diastereo- and Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols in Two Steps from Terminal Alkynes

AU - Miura, Tomoya

AU - Oku, Naoki

AU - Murakami, Masahiro

N1 - Funding Information: This work was supported by MEXT [Grants‐in‐Aids for Scientific Research (S) (15H05756)] and ISHIZUE 2019 of Kyoto University Research Development Program. We thank Mr. J. Nakahashi (Kyoto Univ.) for his contribution at a preliminary stage. Publisher Copyright: © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2019/10/7

Y1 - 2019/10/7

N2 - We report the highly diastereo- and enantioselective preparation of (E)-δ-boryl-substituted anti-homoallylic alcohols in two steps from terminal alkynes. This method consists of a cobalt(II)-catalyzed 1,1-diboration reaction of terminal alkynes with B2pin2 and a palladium(I)-mediated asymmetric allylation reaction of the resulting 1,1-di(boryl)alk-1-enes with aldehydes in the presence of a chiral phosphoric acid. Propyne, which is produced as the byproduct during petroleum refining, could be used as the starting material to construct homoallylic alcohols that are otherwise difficult to synthesize with high stereocontrol.

AB - We report the highly diastereo- and enantioselective preparation of (E)-δ-boryl-substituted anti-homoallylic alcohols in two steps from terminal alkynes. This method consists of a cobalt(II)-catalyzed 1,1-diboration reaction of terminal alkynes with B2pin2 and a palladium(I)-mediated asymmetric allylation reaction of the resulting 1,1-di(boryl)alk-1-enes with aldehydes in the presence of a chiral phosphoric acid. Propyne, which is produced as the byproduct during petroleum refining, could be used as the starting material to construct homoallylic alcohols that are otherwise difficult to synthesize with high stereocontrol.

KW - allylation

KW - asymmetric catalysis

KW - double-bond transposition

KW - homoallylic compounds

KW - palladium

UR - http://www.scopus.com/inward/record.url?scp=85071646534&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85071646534&partnerID=8YFLogxK

U2 - 10.1002/anie.201908299

DO - 10.1002/anie.201908299

M3 - Article

C2 - 31392816

AN - SCOPUS:85071646534

VL - 58

SP - 14620

EP - 14624

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 41

ER -

Diastereo- and Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols in Two Steps from Terminal Alkynes

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this