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Transition-Metal-Catalyzed S–H and Se–H Bonds Addition to Unsaturated Molecules

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Hydrofunctionalization

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

Abstract

This chapter deals with the transition-metal-catalyzed hydrothiolation and hydroselenation of alkynes and allenes and related unsaturated compounds with thiols and selenols. In these reactions, the regio- and/or stereoselectivities of the addition products can be controlled by switching the transition metal catalysts. Metal sulfides and selenides (RE-ML n , E = S, Se, M = Ni, Pd, Rh, Zr, Sm, etc.) play an important role as key catalyst species in these hydrothiolation and hydroselenation. The introduction of carbon monoxide into these hydrothiolation and hydroselenation systems leads to novel carbonylation with simultaneous addition of thio and seleno groups to unsaturated bonds.

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Abbreviations

Ac:

Acetyl

acac:

Acetylacetonate

An:

Actinide

Ar:

Aryl

t-Bu:

tert-butyl

cat:

Catalyst

c-Hex:

Cyclohexyl

coe:

Cyclooctene

cod:

1,5-cyclooctadiene

Cp:

Cyclopentadienyl

Cp*:

Pentamethylcyclopentadienyl

DIOP:

O-2,3-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane

dppp:

1,3-bis(diphenylphosphino)propane

dppf:

1,1’-bis(diphenylphosphino)ferrocene

DTBM-segphos:

5,5’-bis{di(3,5-di-t-butyl-4-methoxyphenyl)phosphino}-4,4’-bi-1,3-benzodioxole

equiv:

Equivalent

GPC:

Gel permeation chromatography

i-Pr:

Isopropyl

IMes:

N,N-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene

Ln:

Lanthanide

ML n :

Transition metal complex (M: metal L: ligand)

mol:

Mole(s)

Me:

Methyl

Ms:

Methanesulfonyl (mesyl)

NHC:

N-heterocyclic carbene ligands

Ph:

Phenyl

py:

Pyridine

R:

Organyl substituent

rt:

Room temperature

SEM:

Scanning electron microscopy

THF:

Tetrahydrofuran

TMS:

Trimethylsilyl

Tp*:

Hydrotris(3,5-dimethylpyrazolyl)borate

p-TsOH:

p-toluenesulfonic acid

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  1. Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Nakaku, Sakai, Osaka, 599-8531, Japan

    Akiya Ogawa

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Correspondence to Akiya Ogawa .

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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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Ogawa, A. (2011). Transition-Metal-Catalyzed S–H and Se–H Bonds Addition to Unsaturated Molecules. In: Ananikov, V., Tanaka, M. (eds) Hydrofunctionalization. Topics in Organometallic Chemistry, vol 43. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3418_2011_19

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