Phosphonate-Directed Catalytic Asymmetric Hydroboration: Delivery of Boron to the More Substituted Carbon, Leading to Chiral Tertiary Benzylic Boronic Esters

Suman Chakrabarty, James M. Takacs

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Phosphonate-directed catalytic asymmetric hydroboration (CAHB) of β-aryl/heteroaryl methylidenes and trisubstituted alkenes by pinacolborane enables facile access to functionalized, chiral tertiary benzylic boronic esters. Hydroboration is catalyzed by a chiral rhodium catalyst prepared in situ from a Rh(I) precursor in combination with a simple TADDOL-derived chiral cyclic monophosphite in a 1:1 ratio. The regio- and stereochemistry arise from the combined effects of the relative disposition of the directing group to the alkene, the alkene substitution pattern, and the necessity of an aryl substituent attached to the alkene. A range of aryl and heteroaryl substituents can be accommodated, and for several chiral substrates, the reactions are efficiently catalyst-controlled, enabling the choice of diastereomeric products as desired. Stereospecific transformations of the chiral boronic ester afford chiral phosphonates bearing a quaternary carbon stereocenter. The synthetic utility of the products is further demonstrated by α-oxidation of the phosphonate, leading to hydroxy- and oxophosphonates; the latter readily undergo elimination/substitution reactions to unmask the phosphonate functionality with the formation of aldehydes, alcohols, esters, amides, acids, and ketones.

Original languageEnglish (US)
Pages (from-to)10530-10536
Number of pages7
JournalACS Catalysis
Volume8
Issue number11
DOIs
StatePublished - Nov 2 2018

Fingerprint

Organophosphonates
Boron
Alkenes
Olefins
Esters
Carbon
Substitution reactions
Bearings (structural)
Rhodium
Stereochemistry
Catalysts
Ketones
Aldehydes
Amides
Alcohols
Oxidation
Acids
Substrates

Keywords

  • asymmetric hydroboration
  • chiral tertiary boronic esters
  • oxophosphonates
  • rhodium catalysis
  • trisubstituted alkene hydroboration

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

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title = "Phosphonate-Directed Catalytic Asymmetric Hydroboration: Delivery of Boron to the More Substituted Carbon, Leading to Chiral Tertiary Benzylic Boronic Esters",
abstract = "Phosphonate-directed catalytic asymmetric hydroboration (CAHB) of β-aryl/heteroaryl methylidenes and trisubstituted alkenes by pinacolborane enables facile access to functionalized, chiral tertiary benzylic boronic esters. Hydroboration is catalyzed by a chiral rhodium catalyst prepared in situ from a Rh(I) precursor in combination with a simple TADDOL-derived chiral cyclic monophosphite in a 1:1 ratio. The regio- and stereochemistry arise from the combined effects of the relative disposition of the directing group to the alkene, the alkene substitution pattern, and the necessity of an aryl substituent attached to the alkene. A range of aryl and heteroaryl substituents can be accommodated, and for several chiral substrates, the reactions are efficiently catalyst-controlled, enabling the choice of diastereomeric products as desired. Stereospecific transformations of the chiral boronic ester afford chiral phosphonates bearing a quaternary carbon stereocenter. The synthetic utility of the products is further demonstrated by α-oxidation of the phosphonate, leading to hydroxy- and oxophosphonates; the latter readily undergo elimination/substitution reactions to unmask the phosphonate functionality with the formation of aldehydes, alcohols, esters, amides, acids, and ketones.",
keywords = "asymmetric hydroboration, chiral tertiary boronic esters, oxophosphonates, rhodium catalysis, trisubstituted alkene hydroboration",
author = "Suman Chakrabarty and Takacs, {James M.}",
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TY - JOUR

T1 - Phosphonate-Directed Catalytic Asymmetric Hydroboration

T2 - Delivery of Boron to the More Substituted Carbon, Leading to Chiral Tertiary Benzylic Boronic Esters

AU - Chakrabarty, Suman

AU - Takacs, James M.

PY - 2018/11/2

Y1 - 2018/11/2

N2 - Phosphonate-directed catalytic asymmetric hydroboration (CAHB) of β-aryl/heteroaryl methylidenes and trisubstituted alkenes by pinacolborane enables facile access to functionalized, chiral tertiary benzylic boronic esters. Hydroboration is catalyzed by a chiral rhodium catalyst prepared in situ from a Rh(I) precursor in combination with a simple TADDOL-derived chiral cyclic monophosphite in a 1:1 ratio. The regio- and stereochemistry arise from the combined effects of the relative disposition of the directing group to the alkene, the alkene substitution pattern, and the necessity of an aryl substituent attached to the alkene. A range of aryl and heteroaryl substituents can be accommodated, and for several chiral substrates, the reactions are efficiently catalyst-controlled, enabling the choice of diastereomeric products as desired. Stereospecific transformations of the chiral boronic ester afford chiral phosphonates bearing a quaternary carbon stereocenter. The synthetic utility of the products is further demonstrated by α-oxidation of the phosphonate, leading to hydroxy- and oxophosphonates; the latter readily undergo elimination/substitution reactions to unmask the phosphonate functionality with the formation of aldehydes, alcohols, esters, amides, acids, and ketones.

AB - Phosphonate-directed catalytic asymmetric hydroboration (CAHB) of β-aryl/heteroaryl methylidenes and trisubstituted alkenes by pinacolborane enables facile access to functionalized, chiral tertiary benzylic boronic esters. Hydroboration is catalyzed by a chiral rhodium catalyst prepared in situ from a Rh(I) precursor in combination with a simple TADDOL-derived chiral cyclic monophosphite in a 1:1 ratio. The regio- and stereochemistry arise from the combined effects of the relative disposition of the directing group to the alkene, the alkene substitution pattern, and the necessity of an aryl substituent attached to the alkene. A range of aryl and heteroaryl substituents can be accommodated, and for several chiral substrates, the reactions are efficiently catalyst-controlled, enabling the choice of diastereomeric products as desired. Stereospecific transformations of the chiral boronic ester afford chiral phosphonates bearing a quaternary carbon stereocenter. The synthetic utility of the products is further demonstrated by α-oxidation of the phosphonate, leading to hydroxy- and oxophosphonates; the latter readily undergo elimination/substitution reactions to unmask the phosphonate functionality with the formation of aldehydes, alcohols, esters, amides, acids, and ketones.

KW - asymmetric hydroboration

KW - chiral tertiary boronic esters

KW - oxophosphonates

KW - rhodium catalysis

KW - trisubstituted alkene hydroboration

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