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Fig. 3 The H NMR (400 MHz, D
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O) spectrum of the equilibrium
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Mechanistic features for aerobic oxidation of alcohols in
III
water catalyzed by (TSPP)Rh . The proposed mechanism
III
for the aerobic oxidation of alcohols catalyzed by (TSPP)Rh
in basic aqueous solution is given in Scheme 1. Displacement
of hydroxide ion by alcohols and subsequent deprotonation to
III
9 H. Li, B. Guan, W. Wang, D. Xing, Z. Fang, X. Wan, L. Yang and
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alkoxide complexes are directly observed in the (TSPP)Rh
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0 N. Komiya, T. Nakae, H. Sato and T. Naota, Chem. Commun.,
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catalyst system. The rate determining step is Rh–alkoxide
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III
with (TSPP)Rh–H/(TSPP)Rh(I) to regenerate (TSPP)Rh
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(
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Scheme 1 Proposed mechanism for catalytic oxidation of alcohols in
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(
In summary, a broad range of alcohol substrates are
III
catalytically oxidized by (TSPP)Rh in water using oxygen
III
as the terminal oxidant. The (TSPP)Rh catalyst system in
¨
(
´
water permits direct observation of alkoxide intermediates and
evaluation of the activation parameters for the rate determining
Rh–alkoxide bC–H elimination. Development of this new
aqueous catalyst system that uses dioxygen without the need
for co-catalysts, suggests that this prototype catalyst system
may find applications in a wide range of ‘‘green’’ oxidation
chemistry.
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This work was supported by NSFC (grants 20841002 and
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(
Notes and references
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This journal is c The Royal Society of Chemistry 2010
Chem. Commun., 2010, 46, 6353–6355 6355