Enantioselective Friedel-Crafts Alkylation Reaction of Indoles with α-Trifluoromethylated β-Nitrostyrenes Catalyzed by Chiral BINOL Metal Phosphate

Ignacio Ibáñez; Mio Kaneko; Yuto Kamei; Ryosuke Tsutsumi; Masahiro Yamanaka; Takahiko Akiyama

doi:10.1021/acscatal.9b01811

Enantioselective Friedel-Crafts Alkylation Reaction of Indoles with α-Trifluoromethylated β-Nitrostyrenes Catalyzed by Chiral BINOL Metal Phosphate

Ignacio Ibáñez, Mio Kaneko, Yuto Kamei, Ryosuke Tsutsumi, Masahiro Yamanaka, Takahiko Akiyama

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

27 Citations (Scopus)

Abstract

An efficient enantioselective Friedel-Crafts alkylation reaction of indoles with α-CF₃-substituted β-nitrostyrenes is disclosed. The key to success is the use of a chiral calcium BINOL bis(phosphate) complex as a Lewis acid catalyst. The reaction gives access to a wide variety of optically active indoles bearing trifluoromethylated all-carbon quaternary stereocenter (up to 20 examples) in high yields (up to 99%) with excellent enantioselectivities (up to 98%) under mild reaction conditions. Nonactivated α-alkyl-β-nitrostyrenes also participated in the Friedel-Crafts alkylation reaction successfully.

Original language	English
Pages (from-to)	6903-6909
Number of pages	7
Journal	ACS Catalysis
Volume	9
Issue number	8
DOIs	https://doi.org/10.1021/acscatal.9b01811
Publication status	Published - 2019 Aug 2
Externally published	Yes

Keywords

Friedel-Crafts alkylation
Indole
metal chiral phosphate
nitroalkene
quaternary carbon center

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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10.1021/acscatal.9b01811

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title = "Enantioselective Friedel-Crafts Alkylation Reaction of Indoles with α-Trifluoromethylated β-Nitrostyrenes Catalyzed by Chiral BINOL Metal Phosphate",

abstract = "An efficient enantioselective Friedel-Crafts alkylation reaction of indoles with α-CF3-substituted β-nitrostyrenes is disclosed. The key to success is the use of a chiral calcium BINOL bis(phosphate) complex as a Lewis acid catalyst. The reaction gives access to a wide variety of optically active indoles bearing trifluoromethylated all-carbon quaternary stereocenter (up to 20 examples) in high yields (up to 99%) with excellent enantioselectivities (up to 98%) under mild reaction conditions. Nonactivated α-alkyl-β-nitrostyrenes also participated in the Friedel-Crafts alkylation reaction successfully.",

keywords = "Friedel-Crafts alkylation, Indole, metal chiral phosphate, nitroalkene, quaternary carbon center",

author = "Ignacio Ib{\'a}{\~n}ez and Mio Kaneko and Yuto Kamei and Ryosuke Tsutsumi and Masahiro Yamanaka and Takahiko Akiyama",

note = "Funding Information: The authors acknowledge a Grant-in-Aid for Scientific Research on Innovative Areas, “Advanced Transformation Organocatalysis”, from MEXT, Japan, as well as Grants-in-Aid for Scientific Research from JSPS (17H03060, 15K05506, 17KT0011), and MEXT-Supported Program for the Strategic Research Foundation at Private Universities. Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",

year = "2019",

month = aug,

day = "2",

doi = "10.1021/acscatal.9b01811",

language = "English",

volume = "9",

pages = "6903--6909",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

number = "8",

}

TY - JOUR

T1 - Enantioselective Friedel-Crafts Alkylation Reaction of Indoles with α-Trifluoromethylated β-Nitrostyrenes Catalyzed by Chiral BINOL Metal Phosphate

AU - Ibáñez, Ignacio

AU - Kaneko, Mio

AU - Kamei, Yuto

AU - Tsutsumi, Ryosuke

AU - Yamanaka, Masahiro

AU - Akiyama, Takahiko

N1 - Funding Information: The authors acknowledge a Grant-in-Aid for Scientific Research on Innovative Areas, “Advanced Transformation Organocatalysis”, from MEXT, Japan, as well as Grants-in-Aid for Scientific Research from JSPS (17H03060, 15K05506, 17KT0011), and MEXT-Supported Program for the Strategic Research Foundation at Private Universities. Publisher Copyright: Copyright © 2019 American Chemical Society.

PY - 2019/8/2

Y1 - 2019/8/2

N2 - An efficient enantioselective Friedel-Crafts alkylation reaction of indoles with α-CF3-substituted β-nitrostyrenes is disclosed. The key to success is the use of a chiral calcium BINOL bis(phosphate) complex as a Lewis acid catalyst. The reaction gives access to a wide variety of optically active indoles bearing trifluoromethylated all-carbon quaternary stereocenter (up to 20 examples) in high yields (up to 99%) with excellent enantioselectivities (up to 98%) under mild reaction conditions. Nonactivated α-alkyl-β-nitrostyrenes also participated in the Friedel-Crafts alkylation reaction successfully.

AB - An efficient enantioselective Friedel-Crafts alkylation reaction of indoles with α-CF3-substituted β-nitrostyrenes is disclosed. The key to success is the use of a chiral calcium BINOL bis(phosphate) complex as a Lewis acid catalyst. The reaction gives access to a wide variety of optically active indoles bearing trifluoromethylated all-carbon quaternary stereocenter (up to 20 examples) in high yields (up to 99%) with excellent enantioselectivities (up to 98%) under mild reaction conditions. Nonactivated α-alkyl-β-nitrostyrenes also participated in the Friedel-Crafts alkylation reaction successfully.

KW - Friedel-Crafts alkylation

KW - Indole

KW - metal chiral phosphate

KW - nitroalkene

KW - quaternary carbon center

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JO - ACS Catalysis

JF - ACS Catalysis

SN - 2155-5435

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Enantioselective Friedel-Crafts Alkylation Reaction of Indoles with α-Trifluoromethylated β-Nitrostyrenes Catalyzed by Chiral BINOL Metal Phosphate

Abstract

Keywords

ASJC Scopus subject areas

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