Manganese-catalyzed directed methylation of C(sp2)-H bonds at 25 °C with high catalytic turnover

Takenari Sato; Takumi Yoshida; Hamad H. Al Mamari; Laurean Ilies; Eiichi Nakamura

doi:10.1021/acs.orglett.7b02778

Manganese-catalyzed directed methylation of C(sp²)-H bonds at 25 °C with high catalytic turnover

Takenari Sato, Takumi Yoshida, Hamad H. Al Mamari, Laurean Ilies^*, Eiichi Nakamura

^*Corresponding author for this work

Chemistry

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

50 Citations (Scopus)

Abstract

We report here a manganese-catalyzed C-H methylation reaction of considerable substrate scope, using MeMgBr, a catalytic amount of MnCl₂· 2LiCl, and an organic dihalide oxidant. The reaction features ambient temperature, low catalyst loading, typically 1%, high catalytic turnover reaching 5.9 × 10³, and no need for an extraneous ligand and illustrates a unique catalytic use of simple manganese salts for C-H activation, which so far has relied on catalysis by manganese carbonyls.

Original language	English
Pages (from-to)	5458-5461
Number of pages	4
Journal	Organic Letters
Volume	19
Issue number	19
DOIs	https://doi.org/10.1021/acs.orglett.7b02778
Publication status	Published - Oct 6 2017

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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10.1021/acs.orglett.7b02778

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title = "Manganese-catalyzed directed methylation of C(sp2)-H bonds at 25 °C with high catalytic turnover",

abstract = "We report here a manganese-catalyzed C-H methylation reaction of considerable substrate scope, using MeMgBr, a catalytic amount of MnCl2· 2LiCl, and an organic dihalide oxidant. The reaction features ambient temperature, low catalyst loading, typically 1%, high catalytic turnover reaching 5.9 × 103, and no need for an extraneous ligand and illustrates a unique catalytic use of simple manganese salts for C-H activation, which so far has relied on catalysis by manganese carbonyls.",

author = "Takenari Sato and Takumi Yoshida and {Al Mamari}, {Hamad H.} and Laurean Ilies and Eiichi Nakamura",

note = "Funding Information: We thank Dr. Rui Shang for helpful discussions (University of Tokyo), Yuki Itabashi for crystallographic analysis (University of Tokyo), and MEXT for financial support (Japan Agency for Science and Technology; CREST; JPMJCR14L4, and Grant-in-Aid no. 15H05754 to E.N.). H.A.M. thanks the Office of International Cooperation at Sultan Qaboos University for an official visit to the University of Tokyo. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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doi = "10.1021/acs.orglett.7b02778",

language = "English",

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journal = "Organic Letters",

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T1 - Manganese-catalyzed directed methylation of C(sp2)-H bonds at 25 °C with high catalytic turnover

AU - Sato, Takenari

AU - Yoshida, Takumi

AU - Al Mamari, Hamad H.

AU - Ilies, Laurean

AU - Nakamura, Eiichi

N1 - Funding Information: We thank Dr. Rui Shang for helpful discussions (University of Tokyo), Yuki Itabashi for crystallographic analysis (University of Tokyo), and MEXT for financial support (Japan Agency for Science and Technology; CREST; JPMJCR14L4, and Grant-in-Aid no. 15H05754 to E.N.). H.A.M. thanks the Office of International Cooperation at Sultan Qaboos University for an official visit to the University of Tokyo. Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/10/6

Y1 - 2017/10/6

N2 - We report here a manganese-catalyzed C-H methylation reaction of considerable substrate scope, using MeMgBr, a catalytic amount of MnCl2· 2LiCl, and an organic dihalide oxidant. The reaction features ambient temperature, low catalyst loading, typically 1%, high catalytic turnover reaching 5.9 × 103, and no need for an extraneous ligand and illustrates a unique catalytic use of simple manganese salts for C-H activation, which so far has relied on catalysis by manganese carbonyls.

AB - We report here a manganese-catalyzed C-H methylation reaction of considerable substrate scope, using MeMgBr, a catalytic amount of MnCl2· 2LiCl, and an organic dihalide oxidant. The reaction features ambient temperature, low catalyst loading, typically 1%, high catalytic turnover reaching 5.9 × 103, and no need for an extraneous ligand and illustrates a unique catalytic use of simple manganese salts for C-H activation, which so far has relied on catalysis by manganese carbonyls.

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DO - 10.1021/acs.orglett.7b02778

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JO - Organic Letters

JF - Organic Letters

IS - 19

ER -

Manganese-catalyzed directed methylation of C(sp²)-H bonds at 25 °C with high catalytic turnover

Abstract

ASJC Scopus subject areas

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