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Transition-Metal-Catalyzed Cross-Couplings through Carbene Migratory Insertion
Ying Xia1, Di Qiu1, Jianbo Wang1
1Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking University , Beijing 100871, China.
Chemical Reviews
|November 2, 2017
Summary
Transition-metal catalysts enable new cross-coupling reactions using diazo compounds. This carbene-based approach facilitates C-C bond formation and expands synthetic possibilities in organic chemistry.
Area of Science:
- Organic Chemistry
- Catalysis
Background:
- Transition-metal-catalyzed cross-coupling reactions are vital in organic synthesis.
- Expanding coupling partner scope is a key research objective.
Purpose of the Study:
- To review advancements in transition-metal-catalyzed cross-coupling reactions involving diazo compounds since 2001.
- To highlight the utility of diazo compounds as nucleophilic partners.
Main Methods:
- Formation of organometallic species via various pathways (e.g., C-H activation, oxidative addition).
- Reaction of organometallic species with diazo substrates to form metal carbene intermediates.
- Carbene migratory insertion to form C-C bonds.
Main Results:
- Diazo compounds and N-tosylhydrazones serve as effective nucleophilic coupling partners.
- Diverse transition metals (Pd, Cu, Rh, Ni, Co, Ir) catalyze these reactions.
- The methodology extends beyond diazo compounds and enables cascade processes.
Conclusions:
- Carbene-based cross-coupling reactions offer a versatile platform for C-C bond formation.
- Significant progress has been made in broadening the scope and applications of these reactions.
- This approach continues to evolve with new substrates and cascade sequences.
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