Abstract

Catalysis of cross-coupling reactions under phosphane-free conditions represents an important ongoing challenge. Although transition metal complexes based on the thiosemicarbazone unit have been known for a very long time, their use in homogeneous catalysis has been studied only relatively recently. In particular, reports of cross-coupling catalytic reactions with such complexes have appeared only in the last 15 years. This review provides a survey of the research in this area and a discussion of the prospects for future developments.

Highlights

  • Catalysis by means of transition metal complexes is a well-established tool for the organic chemist, and the continued interest in the field has led to increasingly more effective and efficient systems for carrying out a wide range of reactions, both on a laboratory and on an industrial scale.The benefits of transition metal catalysis are that the reactions are often very clean and have very high turnovers, meaning that waste products are kept to a minimum, which is one of the precepts of Green Chemistry

  • Research in the area of transition metal catalysed carbon–carbon and carbon–heteroatom coupling reactions has led to a wide variety of very efficient and useful procedures which are most often known by the names of the scientists who pioneered their use such as Suzuki–Miyaura, Mizoroki–Heck, Negishi, Sonogashira, Kumada–Tamao–Corriu, Migita–Kosugi–Stille, Tsuji–Trost, Buchwald–Hartwig [1,2,3,4,5,6,7,8,9]

  • Phosphane ligands have traditionally been the ligands of choice for transition metal catalysis and so for coupling reactions

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Summary

Introduction

Catalysis by means of transition metal complexes is a well-established tool for the organic chemist, and the continued interest in the field has led to increasingly more effective and efficient systems for carrying out a wide range of reactions, both on a laboratory and on an industrial scale. Research in the area of transition metal catalysed carbon–carbon and carbon–heteroatom coupling reactions has led to a wide variety of very efficient and useful procedures which are most often known by the names of the scientists who pioneered their use such as Suzuki–Miyaura, Mizoroki–Heck, Negishi, Sonogashira, Kumada–Tamao–Corriu, Migita–Kosugi–Stille, Tsuji–Trost, Buchwald–Hartwig [1,2,3,4,5,6,7,8,9]. This versatility of coordination, together with the relative ease with which these ligands can oftenThis be prepared, provided a considerable impetus into the study their these metalligands complexes, versatilityhas of coordination, together with the relative ease withofwhich can often be prepared, has provided a considerable impetus into the study of their metal complexes, and and it can be exploited for the development of new which often be prepared,how has provided a considerable impetus into the study ofcatalysts. This aspect aspect is very much in its infancy and the present review will attempt to highlight the most significant studies in this area

Mizoroki–Heck
Representative
Heck reaction ofin with styrene catalysed by complex 1a
The tetradentate coordination was verified
Suzuki–Miyaura and Related Reactions
Representative as catalysts catalysts for for the the Suzuki–Miyaura
22. Suzuki of aryl bromides with substituted phenylboronic acids catalysed by
11. Microwave-promoted
POa4temperature
14. Suzuki
17. Suzuki
20. Suzuki reaction of bromides with phenylboronic acid catalysed by complex
21. Aqueous
OEtOH-H
Sonogashira and Related
Suzuki–Miyaura reactions by thiosemicarbazone complexes:
Sonogashira and Related Reactions
N using a catalyst loading
27. Sonogashira
Kumada–Tamao–Corriu Reaction
Carbon–Heteroatom Coupling Reactions
Figures and
35. Classic
38. Buchwald–Hartwig
39. N-alkylation
OH and primary amines ferrocenylCH amines
Immobilised and Heterogeneous Catalysts
43. Ulmann
Findings
Future Prospects
Full Text
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