Electronic and Steric Tuning of an Atropisomeric Disulfoxide Ligand Motif and Its Use in the Rh(I)-Catalyzed Addition Reactions of Boronic Acids to a Wide Range of Acceptors

Guang Zhen Zhao, Daven Foster, Gellért Sipos, Pengchao Gao, Brian W. Skelton, Alexandre N. Sobolev, Reto Dorta

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Abstract

A novel chiral disulfoxide ligand pair bearing fluorine atoms at the 6 and 6′ position of its atropisomeric backbone, (M,S,S)- and (P,S,S)-p-Tol-6F-BIPHESO, was synthesized. Complexation to a rhodium(I) precursor gave rise to μ-Cl- and μ-OH-bridged rhodium dimer complexes incorporating the new (M,S,S)-p-Tol-6F-BIPHESO ligand, while its sibling (P,S,S)-p-Tol-6F-BIPHESO was not complexed efficiently to the rhodium precursor. The performance of this disulfoxide ligand [(M,S,S)-p-Tol-6F-BIPHESO] in catalysis was tested in both 1,4- and 1,2-addition reactions of arylboronic acids. We show that addition to both cyclic and acyclic enones as well as N-tosylarylimines proceeds with high yields and high enantioselectivities to give the corresponding products. The synthesis of enantiomerically pure p-Tol-6F-BIPHESO is straightforward and inexpensive which, together with the high catalytic performance and wide substrate scope for these addition reactions, makes it a very attractive alternative to more classical chiral ligand entities.

Original languageEnglish
Pages (from-to)9741-9755
Number of pages15
JournalJournal of Organic Chemistry
Volume83
Issue number17
DOIs
Publication statusPublished - 7 Sep 2018

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Boronic Acids
Addition reactions
Rhodium
Tuning
Ligands
Bearings (structural)
Fluorine
Enantioselectivity
Complexation
Dimers
Catalysis
Atoms
Acids
Substrates

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@article{a1c5dfbbf1e847bcb20880c8d6153163,
title = "Electronic and Steric Tuning of an Atropisomeric Disulfoxide Ligand Motif and Its Use in the Rh(I)-Catalyzed Addition Reactions of Boronic Acids to a Wide Range of Acceptors",
abstract = "A novel chiral disulfoxide ligand pair bearing fluorine atoms at the 6 and 6′ position of its atropisomeric backbone, (M,S,S)- and (P,S,S)-p-Tol-6F-BIPHESO, was synthesized. Complexation to a rhodium(I) precursor gave rise to μ-Cl- and μ-OH-bridged rhodium dimer complexes incorporating the new (M,S,S)-p-Tol-6F-BIPHESO ligand, while its sibling (P,S,S)-p-Tol-6F-BIPHESO was not complexed efficiently to the rhodium precursor. The performance of this disulfoxide ligand [(M,S,S)-p-Tol-6F-BIPHESO] in catalysis was tested in both 1,4- and 1,2-addition reactions of arylboronic acids. We show that addition to both cyclic and acyclic enones as well as N-tosylarylimines proceeds with high yields and high enantioselectivities to give the corresponding products. The synthesis of enantiomerically pure p-Tol-6F-BIPHESO is straightforward and inexpensive which, together with the high catalytic performance and wide substrate scope for these addition reactions, makes it a very attractive alternative to more classical chiral ligand entities.",
author = "Zhao, {Guang Zhen} and Daven Foster and Gell{\'e}rt Sipos and Pengchao Gao and Skelton, {Brian W.} and Sobolev, {Alexandre N.} and Reto Dorta",
year = "2018",
month = "9",
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doi = "10.1021/acs.joc.8b01269",
language = "English",
volume = "83",
pages = "9741--9755",
journal = "The Journal of Organic Chemistry",
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publisher = "American Chemical Society",
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T1 - Electronic and Steric Tuning of an Atropisomeric Disulfoxide Ligand Motif and Its Use in the Rh(I)-Catalyzed Addition Reactions of Boronic Acids to a Wide Range of Acceptors

AU - Zhao, Guang Zhen

AU - Foster, Daven

AU - Sipos, Gellért

AU - Gao, Pengchao

AU - Skelton, Brian W.

AU - Sobolev, Alexandre N.

AU - Dorta, Reto

PY - 2018/9/7

Y1 - 2018/9/7

N2 - A novel chiral disulfoxide ligand pair bearing fluorine atoms at the 6 and 6′ position of its atropisomeric backbone, (M,S,S)- and (P,S,S)-p-Tol-6F-BIPHESO, was synthesized. Complexation to a rhodium(I) precursor gave rise to μ-Cl- and μ-OH-bridged rhodium dimer complexes incorporating the new (M,S,S)-p-Tol-6F-BIPHESO ligand, while its sibling (P,S,S)-p-Tol-6F-BIPHESO was not complexed efficiently to the rhodium precursor. The performance of this disulfoxide ligand [(M,S,S)-p-Tol-6F-BIPHESO] in catalysis was tested in both 1,4- and 1,2-addition reactions of arylboronic acids. We show that addition to both cyclic and acyclic enones as well as N-tosylarylimines proceeds with high yields and high enantioselectivities to give the corresponding products. The synthesis of enantiomerically pure p-Tol-6F-BIPHESO is straightforward and inexpensive which, together with the high catalytic performance and wide substrate scope for these addition reactions, makes it a very attractive alternative to more classical chiral ligand entities.

AB - A novel chiral disulfoxide ligand pair bearing fluorine atoms at the 6 and 6′ position of its atropisomeric backbone, (M,S,S)- and (P,S,S)-p-Tol-6F-BIPHESO, was synthesized. Complexation to a rhodium(I) precursor gave rise to μ-Cl- and μ-OH-bridged rhodium dimer complexes incorporating the new (M,S,S)-p-Tol-6F-BIPHESO ligand, while its sibling (P,S,S)-p-Tol-6F-BIPHESO was not complexed efficiently to the rhodium precursor. The performance of this disulfoxide ligand [(M,S,S)-p-Tol-6F-BIPHESO] in catalysis was tested in both 1,4- and 1,2-addition reactions of arylboronic acids. We show that addition to both cyclic and acyclic enones as well as N-tosylarylimines proceeds with high yields and high enantioselectivities to give the corresponding products. The synthesis of enantiomerically pure p-Tol-6F-BIPHESO is straightforward and inexpensive which, together with the high catalytic performance and wide substrate scope for these addition reactions, makes it a very attractive alternative to more classical chiral ligand entities.

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U2 - 10.1021/acs.joc.8b01269

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