Dynamic Thermodynamic Resolution of Racemic 1,1′-Binaphthyl-2,2′-diol (BINOL)

Omer Shaashua; Dennis Pollok; Alina Dyadyuk; Alexander I. Shames; Siegfried R. Waldvogel; Doron Pappo

doi:10.1021/acs.orglett.4c00520

Dynamic Thermodynamic Resolution of Racemic 1,1′-Binaphthyl-2,2′-diol (BINOL)

Omer Shaashua, Dennis Pollok, Alina Dyadyuk, Alexander I. Shames, Siegfried R. Waldvogel, Doron Pappo

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

1 Scopus citations

Abstract

A dynamic thermodynamic resolution method for converting (R/S)-BINOL (1,1′-binaphthyl-2,2′-diol) into (R)-BINOL in 100% theoretical yield is reported. This technique involves mixing (R/S)-BINOL with N-benzyl cinchonidinium bromide (1 equiv) and a [Cu₂(tmeda)₂(μ-OH)₂]Br₂ (2.5 mol %) redox catalyst in acetonitrile. In the background of this process is the observation that the energy for atropoisomerization decreases significantly when an electron is removed from BINOL. Therefore, it is possible to convert both enantiomers into the thermodynamically favorable [N-benzyl cinchonidinium bromide·(R)-BINOL] adduct.

Original language	English
Pages (from-to)	2129-2134
Number of pages	6
Journal	Organic Letters
Volume	26
Issue number	10
DOIs	https://doi.org/10.1021/acs.orglett.4c00520
State	Published - 15 Mar 2024

ASJC Scopus subject areas

Biochemistry
Physical and Theoretical Chemistry
Organic Chemistry

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title = "Dynamic Thermodynamic Resolution of Racemic 1,1′-Binaphthyl-2,2′-diol (BINOL)",

abstract = "A dynamic thermodynamic resolution method for converting (R/S)-BINOL (1,1′-binaphthyl-2,2′-diol) into (R)-BINOL in 100% theoretical yield is reported. This technique involves mixing (R/S)-BINOL with N-benzyl cinchonidinium bromide (1 equiv) and a [Cu2(tmeda)2(μ-OH)2]Br2 (2.5 mol %) redox catalyst in acetonitrile. In the background of this process is the observation that the energy for atropoisomerization decreases significantly when an electron is removed from BINOL. Therefore, it is possible to convert both enantiomers into the thermodynamically favorable [N-benzyl cinchonidinium bromide·(R)-BINOL] adduct.",

author = "Omer Shaashua and Dennis Pollok and Alina Dyadyuk and Shames, {Alexander I.} and Waldvogel, {Siegfried R.} and Doron Pappo",

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T1 - Dynamic Thermodynamic Resolution of Racemic 1,1′-Binaphthyl-2,2′-diol (BINOL)

AU - Shaashua, Omer

AU - Pollok, Dennis

AU - Dyadyuk, Alina

AU - Shames, Alexander I.

AU - Waldvogel, Siegfried R.

AU - Pappo, Doron

PY - 2024/3/15

Y1 - 2024/3/15

N2 - A dynamic thermodynamic resolution method for converting (R/S)-BINOL (1,1′-binaphthyl-2,2′-diol) into (R)-BINOL in 100% theoretical yield is reported. This technique involves mixing (R/S)-BINOL with N-benzyl cinchonidinium bromide (1 equiv) and a [Cu2(tmeda)2(μ-OH)2]Br2 (2.5 mol %) redox catalyst in acetonitrile. In the background of this process is the observation that the energy for atropoisomerization decreases significantly when an electron is removed from BINOL. Therefore, it is possible to convert both enantiomers into the thermodynamically favorable [N-benzyl cinchonidinium bromide·(R)-BINOL] adduct.

AB - A dynamic thermodynamic resolution method for converting (R/S)-BINOL (1,1′-binaphthyl-2,2′-diol) into (R)-BINOL in 100% theoretical yield is reported. This technique involves mixing (R/S)-BINOL with N-benzyl cinchonidinium bromide (1 equiv) and a [Cu2(tmeda)2(μ-OH)2]Br2 (2.5 mol %) redox catalyst in acetonitrile. In the background of this process is the observation that the energy for atropoisomerization decreases significantly when an electron is removed from BINOL. Therefore, it is possible to convert both enantiomers into the thermodynamically favorable [N-benzyl cinchonidinium bromide·(R)-BINOL] adduct.

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JO - Organic Letters

JF - Organic Letters

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ER -

Dynamic Thermodynamic Resolution of Racemic 1,1′-Binaphthyl-2,2′-diol (BINOL)

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