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Synfacts 2022; 18(09): 1001
DOI: 10.1055/s-0041-1738682
Metals in Synthesis

Cobalt-Catalyzed Hydrohydroxylation of Olefins Using Molecular Oxygen – The Mukaiyama Hydration

Contributor(s):
Mark Lautens
,
Austin D. Marchese
Isayama S, Mukaiyama T. * Mitsui Petrochemical Industries, Ltd., japan
A New Method for Preparation of Alcohols from Olefins with Molecular Oxygen and Phenylsilane by the Use of Bis(acetylacetonato)cobalt(II).

Chem. Lett. 1989;
18: 1071-1074
DOI: 10.1246/cl.1989.1071.
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Key words

Mukaiyama hydration - cobalt catalysis - oxygen - olefins

Significance

In 1989, Isayama and Mukaiyama reported the room-temperature Markovnikov hydration of olefins using low loadings of Co(acac)2, phenylsilane and molecular oxygen, more commonly known as the ‘Mukaiyama hydration’. The Mukaiyama hydration has been widely used in total synthesis and is still one of the most effective strategies to enable a Markovnikov hydration of alkenes.


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Review

J. E. Zweig, D. E. Kim, T. R. Newhouse Chem. Rev. 2017, 117, 11680–11752.


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Comment

Previous cobalt-catalyzed hydration protocols used 2° alcohols as the hydride source; however, they required a higher catalyst load and temperature. The reaction mechanism features a 2° radical, which captures O2. This generates the key Co(III)peroxy species, which is reduced by the silane. Notably, the authors were able to obtain silylperoxy species using Ph2SiH2 or Et2SiH2.


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Review

S. W. M. Crossley, C. Obradors, R. M. ­Martinez, R. A. Shenvi Chem. Rev. 2016, 116, 8912–9000.


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Publication History

Article published online:
18 August 2022

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