Enantioselective Synthesis of Biaryl Atropisomers via the Addition of Thiophenols into Aryl-Naphthoquinones

Sean M. Maddox; Gregory A. Dawson; Nicholas C. Rochester; Arianna B. Ayonon; Curtis E. Moore; Arnold L. Rheingold; Jeffrey L. Gustafson

doi:10.1021/acscatal.8b00906

Enantioselective Synthesis of Biaryl Atropisomers via the Addition of Thiophenols into Aryl-Naphthoquinones

Sean M. Maddox
, Gregory A. Dawson
, Nicholas C. Rochester
, Arianna B. Ayonon
, Curtis E. Moore
, Arnold L. Rheingold
, Jeffrey L. Gustafson

Chemistry

San Diego State University
University of California at San Diego

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

39 Scopus citations

Abstract

We report a cinchona alkaloid catalyzed addition of thiophenol into rapidly interconverting aryl-naphthoquinones, resulting in stable biaryl atropisomers upon reductive methylation. An array of thiophenols and naphthoquinone substrates were evaluated, and we observed selectivities up to 98.5:1.5 e.r. Control of the quinone redox properties allowed us to study the stereochemical stabilities of each oxidation state of the substrates. The resulting enantioenriched products can also be moved on via an S_NAr-like reaction sequence to arrive at stable derivatives with excellent enantioretention.

Original language	English
Pages (from-to)	5443-5447
Number of pages	5
Journal	ACS Catalysis
Volume	8
Issue number	6
DOIs	https://doi.org/10.1021/acscatal.8b00906
State	Published - Jun 1 2018

Keywords

aryl-naphthoquinone
atroposelective
biaryl atropisomers
cinchona alkaloid
thiophenol

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10.1021/acscatal.8b00906

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title = "Enantioselective Synthesis of Biaryl Atropisomers via the Addition of Thiophenols into Aryl-Naphthoquinones",

abstract = "We report a cinchona alkaloid catalyzed addition of thiophenol into rapidly interconverting aryl-naphthoquinones, resulting in stable biaryl atropisomers upon reductive methylation. An array of thiophenols and naphthoquinone substrates were evaluated, and we observed selectivities up to 98.5:1.5 e.r. Control of the quinone redox properties allowed us to study the stereochemical stabilities of each oxidation state of the substrates. The resulting enantioenriched products can also be moved on via an SNAr-like reaction sequence to arrive at stable derivatives with excellent enantioretention.",

keywords = "aryl-naphthoquinone, atroposelective, biaryl atropisomers, cinchona alkaloid, thiophenol",

author = "Maddox, \{Sean M.\} and Dawson, \{Gregory A.\} and Rochester, \{Nicholas C.\} and Ayonon, \{Arianna B.\} and Moore, \{Curtis E.\} and Rheingold, \{Arnold L.\} and Gustafson, \{Jeffrey L.\}",

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year = "2018",

month = jun,

day = "1",

doi = "10.1021/acscatal.8b00906",

language = "English",

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T1 - Enantioselective Synthesis of Biaryl Atropisomers via the Addition of Thiophenols into Aryl-Naphthoquinones

AU - Maddox, Sean M.

AU - Dawson, Gregory A.

AU - Rochester, Nicholas C.

AU - Ayonon, Arianna B.

AU - Moore, Curtis E.

AU - Rheingold, Arnold L.

AU - Gustafson, Jeffrey L.

PY - 2018/6/1

Y1 - 2018/6/1

N2 - We report a cinchona alkaloid catalyzed addition of thiophenol into rapidly interconverting aryl-naphthoquinones, resulting in stable biaryl atropisomers upon reductive methylation. An array of thiophenols and naphthoquinone substrates were evaluated, and we observed selectivities up to 98.5:1.5 e.r. Control of the quinone redox properties allowed us to study the stereochemical stabilities of each oxidation state of the substrates. The resulting enantioenriched products can also be moved on via an SNAr-like reaction sequence to arrive at stable derivatives with excellent enantioretention.

AB - We report a cinchona alkaloid catalyzed addition of thiophenol into rapidly interconverting aryl-naphthoquinones, resulting in stable biaryl atropisomers upon reductive methylation. An array of thiophenols and naphthoquinone substrates were evaluated, and we observed selectivities up to 98.5:1.5 e.r. Control of the quinone redox properties allowed us to study the stereochemical stabilities of each oxidation state of the substrates. The resulting enantioenriched products can also be moved on via an SNAr-like reaction sequence to arrive at stable derivatives with excellent enantioretention.

KW - aryl-naphthoquinone

KW - atroposelective

KW - biaryl atropisomers

KW - cinchona alkaloid

KW - thiophenol

UR - https://www.scopus.com/pages/publications/85047061630

U2 - 10.1021/acscatal.8b00906

DO - 10.1021/acscatal.8b00906

M3 - Article

AN - SCOPUS:85047061630

SN - 2155-5435

VL - 8

SP - 5443

EP - 5447

JO - ACS Catalysis

JF - ACS Catalysis

IS - 6

ER -

Enantioselective Synthesis of Biaryl Atropisomers via the Addition of Thiophenols into Aryl-Naphthoquinones

Abstract

Keywords

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