In Situ Formation of Allyl Ketones via Hiyama-Nozaki Reactions Followed by a Chromium-Mediated Oppenauer Oxidation

H.S. Schrekker; M.W.G. de Bolster; R.V.A. Orru; L.A. Wessjohann

doi:10.1021/jo001750u

In Situ Formation of Allyl Ketones via Hiyama-Nozaki Reactions Followed by a Chromium-Mediated Oppenauer Oxidation

H.S. Schrekker, M.W.G. de Bolster, R.V.A. Orru, L.A. Wessjohann

Research output: Contribution to Journal › Article › Academic › peer-review

Abstract

In Hiyama-Nozaki reactions of allylchromium with aldehydes the expected products are homo-allylalcohols. However, oxidation products derived from these, predominantly allyl ketones, can be common side products. This can be explained by an Oppenauer-(Meerwein-Ponndorf-Verley)-type mechanism (OMPV-reaction). The amount of oxidation is strongly dependent on the substitution pattern of the reaction partners and the reaction conditions. An appropriate choice of these can lead to preferential formation of ketones instead of the alcohols. In addition to its synthetic usefulness, the oxidation-reduction equilibrium is of the utmost importance for the design of enantioselective Hiyama-Nozaki reactions because it is also a potential racemization pathway.

Original language	English
Pages (from-to)	1975-1981
Number of pages	6
Journal	Journal of Organic Chemistry
Volume	67
Issue number	7
DOIs	https://doi.org/10.1021/jo001750u
Publication status	Published - 2002

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title = "In Situ Formation of Allyl Ketones via Hiyama-Nozaki Reactions Followed by a Chromium-Mediated Oppenauer Oxidation",

abstract = "In Hiyama-Nozaki reactions of allylchromium with aldehydes the expected products are homo-allylalcohols. However, oxidation products derived from these, predominantly allyl ketones, can be common side products. This can be explained by an Oppenauer-(Meerwein-Ponndorf-Verley)-type mechanism (OMPV-reaction). The amount of oxidation is strongly dependent on the substitution pattern of the reaction partners and the reaction conditions. An appropriate choice of these can lead to preferential formation of ketones instead of the alcohols. In addition to its synthetic usefulness, the oxidation-reduction equilibrium is of the utmost importance for the design of enantioselective Hiyama-Nozaki reactions because it is also a potential racemization pathway.",

author = "H.S. Schrekker and \{de Bolster\}, M.W.G. and R.V.A. Orru and L.A. Wessjohann",

year = "2002",

doi = "10.1021/jo001750u",

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T1 - In Situ Formation of Allyl Ketones via Hiyama-Nozaki Reactions Followed by a Chromium-Mediated Oppenauer Oxidation

AU - Schrekker, H.S.

AU - de Bolster, M.W.G.

AU - Orru, R.V.A.

AU - Wessjohann, L.A.

PY - 2002

Y1 - 2002

N2 - In Hiyama-Nozaki reactions of allylchromium with aldehydes the expected products are homo-allylalcohols. However, oxidation products derived from these, predominantly allyl ketones, can be common side products. This can be explained by an Oppenauer-(Meerwein-Ponndorf-Verley)-type mechanism (OMPV-reaction). The amount of oxidation is strongly dependent on the substitution pattern of the reaction partners and the reaction conditions. An appropriate choice of these can lead to preferential formation of ketones instead of the alcohols. In addition to its synthetic usefulness, the oxidation-reduction equilibrium is of the utmost importance for the design of enantioselective Hiyama-Nozaki reactions because it is also a potential racemization pathway.

AB - In Hiyama-Nozaki reactions of allylchromium with aldehydes the expected products are homo-allylalcohols. However, oxidation products derived from these, predominantly allyl ketones, can be common side products. This can be explained by an Oppenauer-(Meerwein-Ponndorf-Verley)-type mechanism (OMPV-reaction). The amount of oxidation is strongly dependent on the substitution pattern of the reaction partners and the reaction conditions. An appropriate choice of these can lead to preferential formation of ketones instead of the alcohols. In addition to its synthetic usefulness, the oxidation-reduction equilibrium is of the utmost importance for the design of enantioselective Hiyama-Nozaki reactions because it is also a potential racemization pathway.

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U2 - 10.1021/jo001750u

DO - 10.1021/jo001750u

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SN - 0022-3263

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SP - 1975

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JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 7

ER -

In Situ Formation of Allyl Ketones via Hiyama-Nozaki Reactions Followed by a Chromium-Mediated Oppenauer Oxidation

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