Recent Advances in Asymmetric Metal-Catalyzed Carbene Transfer from Diazo Compounds Toward Molecular Complexity

doi:10.1016/bs.adomc.2016.08.002

Advances in Organometallic Chemistry

Volume 66, 2016, Pages 33-91

https://doi.org/10.1016/bs.adomc.2016.08.002 Get rights and content

Abstract

The discovery of novel organic transformations via metal-carbene intermediates, generated by metal-catalyzed decomposition of diazo compounds, has become an important method to obtain complex molecules with high degrees of chemo-, regio-, diastereo-, and enantioselectivity. This methodology has provided a series of transformations such as cyclopropanation, cyclopropenation, C–H and heteroatom–hydrogen insertions, ylide formation and its subsequent Wolff rearrangement, 1,2-migration, dimerization, olefination, oligomerization, polymerization, and cross-coupling reactions. In this review, we focused on the most recent advances in synthetic transformations of diazo-based metal-carbene chemistry since 2011 with particular emphasis in their use with complex substrates.

Introduction

Metal-based catalysis for the decomposition of diazo compounds has been known for more than a century.¹ In particular, they have been extensively used as precursors of metal carbenes, a key putative intermediate that is generated from the reaction between a metal complex and a diazo compound via the loss of dinitrogen.

The catalytic cycle for the conversion of a diazo compound to a metal-stabilized carbene, and subsequent transfer of the metal-carbene intermediate to diverse transformations such as cyclopropanation, cyclopropenation, C–H insertions, heteroatom–hydrogen insertions, ylide-forming reactions, 1,2-migration, Wolff rearrangement, dimerization, olefination, oligomerization, polymerization, or cross-coupling reactions are shown in Scheme 1. With the appropriate catalyst design, these transformations afford diverse and complex molecules from simple starting materials accompanied by high degrees of chemo-, regio-, diastereo-, and enantioselectivity.

Recently, this diazo chemistry has been well summarized in a number of excellent reviews.¹ Herein we have focused on the most recent advances in synthetic transformations since 2011 with the hope that this chapter will help to the development of new transformations in the area.

Section snippets

Insertion Reaction

Since carbon–heteroatom (C–X) bonds are ubiquitous and generally are one of the most active parts of organic compounds, the research on construction of C–X bonds is an important process. Transition metal-catalyzed insertion of carbenes ligands, in situ generated from diazo compounds, into the heteroatom–hydrogen (X–H, X = N, O, S, Si, etc.) bonds are the straightforward way to construct the carbon–heteroatom bond. In short, insertion reactions, also known as α,α-substitution reactions of

Cycloadditions

Metal-catalyzed cycloaddition reactions are most important tools for synthesis in organic chemistry enabling them to build carbocyclic and heterocyclic structures. These structures can then be used to develop a broad range of functional materials, including pharmaceuticals, agrochemicals, dyes, and optics. Cycloaddition plays a major role in the synthesis of natural products and biologically active substances. This review provides several examples of metal-catalyzed cycloaddition reactions,

Trapping Tactic

Over the past decades, it has been well established that the transition metal-catalyzed decomposition of diazo compounds can undergo ylide formation which can either be trapped by suitable dipolarophiles, undergo cyclization, or verify a subsequent rearrangement to give heterocycles. The in situ trapping of an active intermediate, generated from metal-carbene intermediates and an X heteroatom (X = N, O, S, etc.), has promoted the discovery of synthetically useful transformations, which allow

Summary

This account describes a summary of influence transformations of diazo compounds catalyzed by transition metal complexes which are widely used in organic synthesis to construct complicated natural or synthetic molecules in an efficient way, most of them with enantiomeric excesses. The past 5 years have been creative in the history of α-diazocarbonyl chemistry, despite the fact that it has been in existence for over a century. The driving force for all of these recent developments has been high

Acknowledgments

We greatly thank the National Natural Science Foundation of China (NSFC) (Grant No. 21332003). We are also grateful to our talented coworkers, whose names are shown in the references, for their outstanding contributions.

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Chapter Two - Recent Advances in Asymmetric Metal-Catalyzed Carbene Transfer from Diazo Compounds Toward Molecular Complexity

Abstract

Introduction

Section snippets

Insertion Reaction

Cycloadditions

Trapping Tactic

Summary

Acknowledgments

Chem Sci

J Org Chem

Angew Chem Int Ed

J Am Chem Soc

Chem Eur J

J Am Chem Soc

Rh-catalyzed intermolecular reactions of α-alkyl-α-diazo carbonyl compounds with selectivity over β-hydride migration

Acc Chem Res

Gold-catalyzed transformations of α-diazocarbonyl compounds: selectivity and diversity

Chem Soc Rev

Alkaloid synthesis via carbenoid intermediates

Curr Org Chem

Chiral dirhodium(II) catalysts for selective metal carbene reactions

Curr Org Chem

Recent advances in C(sp3)–H bond functionalization via metal–carbene insertions

Beilstein J Org Chem

Recent advances in the chemistry of Rh carbenoids: multicomponent reactions of diazocarbonyl compounds

Russ Chem Rev

Modern organic synthesis with α-diazocarbonyl compounds

Chem Rev

C–H bond functionalization based on metal carbene migratory insertion

Chem Commun

Diazoacetate and related metal-stabilized carbene species in MCRs

Multicomp React Org Syn

Iron-catalyzed transformations of diazo compounds

Nat Sci Rev

Novel multicomponent reactions via trapping of protic onium ylides with electrophiles

Acc Chem Res

Reaction of diazo compounds with organoboron compounds

Synthesis

Diazo Compounds and n-tosylhydrazones: novel cross-coupling partners in transition-metal-catalyzed reactions

Acc Chem Res

Catalytic cascade reactions involving metal carbene migratory insertion

ACS Catal

Guiding principles for site selective and stereoselective intermolecular C–H functionalization by donor/acceptor rhodium carbenes

Chem Soc Rev

Intramolecular catalytic asymmetric carbon–hydrogen insertion reactions. Synthetic advantages in total synthesis in comparison with alternative approaches

Org Biomol Chem

Rhodium (II)-catalyzed enantioselective C-H functionalization of indoles

J Am Chem Soc

Asymmetric C—H functionalization of indoles via enantioselective protonation

Acta Chim Sin

Enantioselective palladium-catalyzed C-H functionalization of indoles using an axially chiral 2,2′-bipyridine ligand

Angew Chem Int Ed

Sequential C–H functionalization reactions for the enantioselective synthesis of highly functionalized 2,3-dihydrobenzofurans

J Am Chem Soc

Highly site-selective direct C−H bond functionalization of phenols with α-aryl-α-diazoacetates and diazooxindoles via gold catalysis

J Am Chem Soc

Role of sterically demanding chiral dirhodium catalysts in site-selective C–H functionalization of activated primary C–H bonds

J Am Chem Soc

2,2,2-Trichloroethyl aryldiazoacetates as robust reagents for the enantioselective C–H functionalization of methyl ethers

J Am Chem Soc

Late-stage C–H functionalization of complex alkaloids and drug molecules via intermolecular rhodium-carbenoid insertion

Nat Commun

Concise syntheses of dictyodendrins A and F by a sequential C–H functionalization strategy

J Am Chem Soc

Enantioselective cis-β-lactam synthesis by intramolecular C–H functionalization from enoldiazoacetamides and derivative donor–acceptor cyclopropenes

Chem Sci

Synthesis of benzo-γ-sultams via the Rh-catalyzed aromatic C–H functionalization of diazosulfonamides

Chem Commun

Catalytic asymmetric arylation of α-aryl-α-diazoacetates with aniline derivatives

J Am Chem Soc

Aliphatic C-H to C-C conversion: synthesis of (−)-Cameroonan-7r-ol

J Org Chem

Highly convergent total synthesis of (+)-lithospermic acid via a late-stage intermolecular C-H olefination

J Am Chem Soc

Enantioselective synthesis of (−)-Maoecrystal V by enantiodetermining C−H functionalization

J Am Chem Soc

Highly enantioselective trapping of zwitterionic intermediates by imines

Nat Chem

Enantioselective palladium(II) phosphate catalyzed three-component reactions of pyrrole, diazoesters, and imines

Stereoselective Rh₂(S-IBAZ)₄-catalyzed cyclopropanation of alkenes, alkynes, and allenes: asymmetric synthesis of diacceptor cyclopropylphosphonates and alkylidenecyclopropanes

Rh₂(S-PTTL)₃TPA—a mixed-ligand dirhodium(II) catalyst for enantioselective reactions of α-alkyl-α-diazoesters