Ruthenium(II)-Catalyzed C–H Functionalization Using the Oxazolidinone Heterocycle as a Weakly Coordinating Directing Group: Experimental and Computational Insights

Jamie A. Leitch, Philippe B. Wilson, Claire L. McMullin, Mary F. Mahon, Yunas Bhonoah, Ian H. Williams, Christopher G. Frost

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Abstract

Herein, we report the ruthenium-catalyzed ortho C–H alkenylation of a wide range of N-aryloxazolidinone scaffolds. Alkenylation was achieved with complete monoselectivity with a scope of 27 examples in 2-MeTHF. Yields ranged from 23 to 94%, producing highly decorated oxazolidinone scaffolds. A kinetically relevant C–H cleavage was also observed with a kinetic isotope effect (KIE) of ∼2. Density functional theory calculations provided information about mechanism, detailing the β-hydride elimination as the most energetically challenging step of 13.5 kcal mol–1. In-depth computational kinetic studies also predicted a KIE of 2.17 for C–H cleavage and an intrinsic KIE for the reaction of 2.22, in line with the experimentally observed value.
Original languageEnglish
Pages (from-to)5520-5529
Number of pages10
JournalACS Catalysis
Volume6
Issue number8
Early online date14 Jul 2016
DOIs
Publication statusPublished - 27 Jul 2016

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Oxazolidinones
Ruthenium
Alkenylation
Isotopes
Kinetics
Scaffolds
Hydrides
Density functional theory

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@article{6431c636f72d4070b3bfb9e34465e504,
title = "Ruthenium(II)-Catalyzed C–H Functionalization Using the Oxazolidinone Heterocycle as a Weakly Coordinating Directing Group: Experimental and Computational Insights",
abstract = "Herein, we report the ruthenium-catalyzed ortho C–H alkenylation of a wide range of N-aryloxazolidinone scaffolds. Alkenylation was achieved with complete monoselectivity with a scope of 27 examples in 2-MeTHF. Yields ranged from 23 to 94{\%}, producing highly decorated oxazolidinone scaffolds. A kinetically relevant C–H cleavage was also observed with a kinetic isotope effect (KIE) of ∼2. Density functional theory calculations provided information about mechanism, detailing the β-hydride elimination as the most energetically challenging step of 13.5 kcal mol–1. In-depth computational kinetic studies also predicted a KIE of 2.17 for C–H cleavage and an intrinsic KIE for the reaction of 2.22, in line with the experimentally observed value.",
author = "Leitch, {Jamie A.} and Wilson, {Philippe B.} and McMullin, {Claire L.} and Mahon, {Mary F.} and Yunas Bhonoah and Williams, {Ian H.} and Frost, {Christopher G.}",
year = "2016",
month = "7",
day = "27",
doi = "10.1021/acscatal.6b01370",
language = "English",
volume = "6",
pages = "5520--5529",
journal = "ACS Catalysis",
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publisher = "American Chemical Society",
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TY - JOUR

T1 - Ruthenium(II)-Catalyzed C–H Functionalization Using the Oxazolidinone Heterocycle as a Weakly Coordinating Directing Group: Experimental and Computational Insights

AU - Leitch, Jamie A.

AU - Wilson, Philippe B.

AU - McMullin, Claire L.

AU - Mahon, Mary F.

AU - Bhonoah, Yunas

AU - Williams, Ian H.

AU - Frost, Christopher G.

PY - 2016/7/27

Y1 - 2016/7/27

N2 - Herein, we report the ruthenium-catalyzed ortho C–H alkenylation of a wide range of N-aryloxazolidinone scaffolds. Alkenylation was achieved with complete monoselectivity with a scope of 27 examples in 2-MeTHF. Yields ranged from 23 to 94%, producing highly decorated oxazolidinone scaffolds. A kinetically relevant C–H cleavage was also observed with a kinetic isotope effect (KIE) of ∼2. Density functional theory calculations provided information about mechanism, detailing the β-hydride elimination as the most energetically challenging step of 13.5 kcal mol–1. In-depth computational kinetic studies also predicted a KIE of 2.17 for C–H cleavage and an intrinsic KIE for the reaction of 2.22, in line with the experimentally observed value.

AB - Herein, we report the ruthenium-catalyzed ortho C–H alkenylation of a wide range of N-aryloxazolidinone scaffolds. Alkenylation was achieved with complete monoselectivity with a scope of 27 examples in 2-MeTHF. Yields ranged from 23 to 94%, producing highly decorated oxazolidinone scaffolds. A kinetically relevant C–H cleavage was also observed with a kinetic isotope effect (KIE) of ∼2. Density functional theory calculations provided information about mechanism, detailing the β-hydride elimination as the most energetically challenging step of 13.5 kcal mol–1. In-depth computational kinetic studies also predicted a KIE of 2.17 for C–H cleavage and an intrinsic KIE for the reaction of 2.22, in line with the experimentally observed value.

UR - http://dx.doi.org/10.1021/acscatal.6b01370

U2 - 10.1021/acscatal.6b01370

DO - 10.1021/acscatal.6b01370

M3 - Article

VL - 6

SP - 5520

EP - 5529

JO - ACS Catalysis

JF - ACS Catalysis

SN - 2155-5435

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ER -