Stereoselective synthesis of syn-configured α-allenols by rhodium-catalyzed reaction of alkynyl oxiranes with arylboronic acids

Tomoya Miura; Masahiko Shimada; Paula De Mendoza; Carl Deutsch; Norbert Krause; Masahiro Murakami

doi:10.1021/jo900987w

Stereoselective synthesis of syn-configured α-allenols by rhodium-catalyzed reaction of alkynyl oxiranes with arylboronic acids

Tomoya Miura, Masahiko Shimada, Paula De Mendoza, Carl Deutsch, Norbert Krause, Masahiro Murakami

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

45 Citations (Scopus)

Abstract

(Chemical Equation Presented) A rhodium-catalyzed reaction of alkynyl oxiranes with arylboronic acids affords syn-configured α-allenols with high diastereoselectivity. The reaction is initiated by addition of an arylrhodium(I) species onto the alkyne moiety of the alkynyl oxirane. The resulting alkenylrhodium(I) intermediate undergoes β-oxygen elimination to open the oxirane ring in a syn-selective fashion. Protonolysis of the rhodium(I) alkoxide with arylboronic acid releases the corresponding α-allenol along with the rhodium(I) boronate, which undergoes β-aryl elimination to regenerate the arylrhodium(I) species. The utility of this method is demonstrated by an application to a concise synthesis of (±)-Boivinianin B.

Original language	English
Pages (from-to)	6050-6054
Number of pages	5
Journal	Journal of Organic Chemistry
Volume	74
Issue number	16
DOIs	https://doi.org/10.1021/jo900987w
Publication status	Published - 2009
Externally published	Yes

ASJC Scopus subject areas

Organic Chemistry

Access to Document

10.1021/jo900987w

Cite this

Stereoselective synthesis of syn-configured α-allenols by rhodium-catalyzed reaction of alkynyl oxiranes with arylboronic acids. / Miura, Tomoya; Shimada, Masahiko; De Mendoza, Paula; Deutsch, Carl; Krause, Norbert; Murakami, Masahiro.

In: Journal of Organic Chemistry, Vol. 74, No. 16, 2009, p. 6050-6054.

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

@article{22932012863c4619a535a2e25882e917,

title = "Stereoselective synthesis of syn-configured α-allenols by rhodium-catalyzed reaction of alkynyl oxiranes with arylboronic acids",

abstract = "(Chemical Equation Presented) A rhodium-catalyzed reaction of alkynyl oxiranes with arylboronic acids affords syn-configured α-allenols with high diastereoselectivity. The reaction is initiated by addition of an arylrhodium(I) species onto the alkyne moiety of the alkynyl oxirane. The resulting alkenylrhodium(I) intermediate undergoes β-oxygen elimination to open the oxirane ring in a syn-selective fashion. Protonolysis of the rhodium(I) alkoxide with arylboronic acid releases the corresponding α-allenol along with the rhodium(I) boronate, which undergoes β-aryl elimination to regenerate the arylrhodium(I) species. The utility of this method is demonstrated by an application to a concise synthesis of (±)-Boivinianin B.",

author = "Tomoya Miura and Masahiko Shimada and {De Mendoza}, Paula and Carl Deutsch and Norbert Krause and Masahiro Murakami",

year = "2009",

doi = "10.1021/jo900987w",

language = "English",

volume = "74",

pages = "6050--6054",

journal = "Journal of Organic Chemistry",

issn = "0022-3263",

publisher = "American Chemical Society",

number = "16",

}

TY - JOUR

T1 - Stereoselective synthesis of syn-configured α-allenols by rhodium-catalyzed reaction of alkynyl oxiranes with arylboronic acids

AU - Miura, Tomoya

AU - Shimada, Masahiko

AU - De Mendoza, Paula

AU - Deutsch, Carl

AU - Krause, Norbert

AU - Murakami, Masahiro

PY - 2009

Y1 - 2009

N2 - (Chemical Equation Presented) A rhodium-catalyzed reaction of alkynyl oxiranes with arylboronic acids affords syn-configured α-allenols with high diastereoselectivity. The reaction is initiated by addition of an arylrhodium(I) species onto the alkyne moiety of the alkynyl oxirane. The resulting alkenylrhodium(I) intermediate undergoes β-oxygen elimination to open the oxirane ring in a syn-selective fashion. Protonolysis of the rhodium(I) alkoxide with arylboronic acid releases the corresponding α-allenol along with the rhodium(I) boronate, which undergoes β-aryl elimination to regenerate the arylrhodium(I) species. The utility of this method is demonstrated by an application to a concise synthesis of (±)-Boivinianin B.

AB - (Chemical Equation Presented) A rhodium-catalyzed reaction of alkynyl oxiranes with arylboronic acids affords syn-configured α-allenols with high diastereoselectivity. The reaction is initiated by addition of an arylrhodium(I) species onto the alkyne moiety of the alkynyl oxirane. The resulting alkenylrhodium(I) intermediate undergoes β-oxygen elimination to open the oxirane ring in a syn-selective fashion. Protonolysis of the rhodium(I) alkoxide with arylboronic acid releases the corresponding α-allenol along with the rhodium(I) boronate, which undergoes β-aryl elimination to regenerate the arylrhodium(I) species. The utility of this method is demonstrated by an application to a concise synthesis of (±)-Boivinianin B.

UR - http://www.scopus.com/inward/record.url?scp=70349107247&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=70349107247&partnerID=8YFLogxK

U2 - 10.1021/jo900987w

DO - 10.1021/jo900987w

M3 - Article

AN - SCOPUS:70349107247

VL - 74

SP - 6050

EP - 6054

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 16

ER -

Stereoselective synthesis of syn-configured α-allenols by rhodium-catalyzed reaction of alkynyl oxiranes with arylboronic acids

Abstract

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Cite this