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Article

Highly Efficient C−C Bond-Forming Reactions in Aqueous Media Catalyzed by Monomeric Vanadate Species in an Apatite Framework

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Takayoshi Hara, Satoko Kanai, Kohsuke Mori, Tomoo Mizugaki, Kohki Ebitani, Koichiro Jitsukawa,^† and Kiyotomi Kaneda*

Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531, Japan

J. Org. Chem., 2006, 71 (19), pp 7455–7462

DOI: 10.1021/jo0614745

Publication Date (Web): August 23, 2006

†

Present address: Department of Applied Chemistry, Graduate School of Engineering, Nagoya Institute of Technology, Showa-ku, Nagoya 466-8555, Japan.

Corresponding author. Tel: +81-6-6850-6260. Fax: +81-6-6850-6260.

, kaneda@cheng.es.osaka-u.ac.jp

Abstract

A calcium vanadate apatite (VAp), in which PO₄³^- of hydroxyapatite (HAP), Ca₁₀(PO₄)₆(OH)₂, is completely substituted by VO₄³^- in the apatite framework, was synthesized. Physicochemical analysis of the VAp reveals the presence of isolated VO₄ tetrahedron units with a pentavalent oxidation state. The VAp acts as a high-performance heterogeneous base catalyst for various carbon−carbon bond-forming reactions such as Michael and aldol reactions in aqueous media and the H−D exchange reactions using deuterium oxide. For example, a 200-mmol-scale Michael reaction under triphasic conditions proceeded rapidly, with an extremely high turnover number of up to 260 400 and an excellent turnover frequency of 48 s^-¹. No vanadium leaching was detected during the above reactions, and the catalyst was readily recycled with no loss of activity.

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Published In Issue September 15, 2006
Received July 16, 2006

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Article

Highly Efficient C−C Bond-Forming Reactions in Aqueous Media Catalyzed by Monomeric Vanadate Species in an Apatite Framework

Abstract

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SciFinder Links

History

Recommend & Share

Related Content

Hydroxyapatite-Bound Cationic Ruthenium Complexes as Novel Heterogeneous Lewis Acid Catalysts for Diels−Alder and Aldol Reactions

Rhodium-Catalyzed Coupling of 2-Silylphenylboronic Acids with Alkynes Leading to Benzosiloles: Catalytic Cleavage of the Carbon−Silicon Bond in Trialkylsilyl Groups

Total Synthesis of (−)-Acutumine

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