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The Mechanism for Transition-Metal-Catalyzed Hydrochalcogenation of Unsaturated Organic Molecules

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Hydrofunctionalization

Part of the book series: Topics in Organometallic Chemistry ((TOPORGAN,volume 43))

Abstract

In this chapter, discussions are focused on two types of mechanisms of transition-metal-catalyzed hydrochalcogenation, Type I and Type II, which are classified by the initial behavior of precatalysts. In Type I mechanism, precatalyst M–X (M = Pd, Ni, Zr, Ln, and An) first undergoes protonolysis with REH (E = O, S, and Se) to generate active catalyst M–ER, which then undergoes insertion of alkyne into the M–ER bond (chalcogenometalation) to give 2-chalcogenovinyl complex, followed by protonolysis of M–Cvinyl with REH to produce the product and to regenerate active catalyst M–ER. Type II mechanism starts from oxidative addition of REH (E = S and Se) to complex [M] (M = Pd, Pt, Rh, and Ir) to give chalcogenolato–hydrido complex, [M]H(ER). In the next alkyne insertion, [M]–H insertion (hydrometalation) to give [M](ER)(vinyl) or [M]–E insertion (chalcogenometalation) to give [M]H(2-RE-vinyl) occurs and then reductive elimination of the resulting vinyl [M] complexes yields the product and [M]. Reactions where transition metal catalysts exert as Lewis acid to activate unsaturated bonds and those proceeding through vinylidene intermediates are mentioned only shortly.

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  1. Department of Chemistry, Graduate School of Science and Engineering, Saitama University, 255 Shimo-okubo, Sakura-ku, Saitama, 338-8570, Japan

    Akihiko Ishii & Norio Nakata

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  1. Akihiko Ishii
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  2. Norio Nakata
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Correspondence to Akihiko Ishii .

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  1. , Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences (RAS), Leninsky Prospekt 47, Moscow, 119991, Russia

    Valentine P. Ananikov

  2. , Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503, Japan

    Masato Tanaka

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Ishii, A., Nakata, N. (2011). The Mechanism for Transition-Metal-Catalyzed Hydrochalcogenation of Unsaturated Organic Molecules. In: Ananikov, V., Tanaka, M. (eds) Hydrofunctionalization. Topics in Organometallic Chemistry, vol 43. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3418_2011_16

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