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Synthesis
DOI: 10.1055/a-2746-2087
Review

Recent Advances in Transition Metal-Catalyzed Reactions and Synthesis of Isocyanates

Authors

  • Mohsen Rezaei

    1   School of Chemistry, College of Science, University of Tehran, Tehran, Iran (Ringgold ID: RIN48425)

  • Melika Kasmaei

    1   School of Chemistry, College of Science, University of Tehran, Tehran, Iran (Ringgold ID: RIN48425)

  • Ebrahim Kianmehr

    1   School of Chemistry, College of Science, University of Tehran, Tehran, Iran (Ringgold ID: RIN48425)

We gratefully acknowledge the financial support received from the University of Tehran. Additionally, this work is based on research funded by the Iran National Science Foundation (INSF) under project No. 4028705.
Supported by: University of Tehran
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Graphical Abstract

Abstract

Isocyanates are reactive functional groups toward nucleophiles such as amines, alcohols, and thiols, making them valuable intermediates for introducing other functionalities. Amide bonds are prevalent in numerous drugs and natural products. Catalytic C–H and C–X bond activation followed by addition to isocyanates has emerged as an attractive strategy for constructing these bonds, providing a direct and efficient route to incorporate this valuable group. Although isocyanates react with organometallic reagents such as Grignard, organolithium, and organozinc compounds to form amides, these reactions often lack selectivity and control. This review explores the utility of transition metals in the synthesis and reactions of isocyanates. Besides transition metal–catalyzed reactions leading to amides, other transformations such as hydroboration, aminoboration, reduction, and decarboxylative amidation are reviewed. Moreover, transition metal–catalyzed isocyanate reactions for synthesizing nitrogen-containing heterocycles are covered. The synthesis of isocyanates is frequently achieved through in situ rearrangements, particularly via transition-metal-catalyzed Curtius and Lossen rearrangements. Numerous studies demonstrate the versatility and efficiency of these approaches. Additionally, recent applications of cyanate salts and trimethylsilyl isocyanate as cyanatation reagents in the presence of transition metals are discussed, along with plausible mechanisms for each reaction.

Keywords

Transition metals - Organometallic reagents - Nucleophilic addition - Insertion - Hydroboration - Homogeneous catalysis


Publication History

Received: 03 August 2025

Accepted after revision: 12 November 2025

Accepted Manuscript online:
12 November 2025

Article published online:
07 January 2026

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