Generation and Reaction of Metal-Containing Carbonyl Ylides:  Tandem [3+2]-Cycloaddition−Carbene Insertion Leading to Novel Polycyclic Compounds

Iwasawa, Nobuharu; Shido, Masahide; Kusama, Hiroyuki

doi:10.1021/ja010478i

Cited by 153 publications

(57 citation statements)

References 5 publications

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“…15 They also demonstrated the formation of interesting carbenoid-containing carbonyl ylides (tungsten-containing benzopyryliums) generated from 1c in the presence of reactants (Scheme 7b). 16 The dichotomous behavior of the alkyne complex is explained by the rapid equilibrium between an alkyne complex and a carbenoid-containing carbonyl ylide generated via 6-endo-dig cyclization, and the irreversible formation of benzopyranylidene complexes generated via a vinylidene complex.…”

Section: Cyclic Carbene Complexes From Conjugated Alkynesmentioning

confidence: 99%

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Development of Catalytic Carbene Transfer Reactions Using Alkynes as a Source of Carbenes

Ohe

Miki

2009

J. Synth. Org. Chem. Jpn.

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Abstract:The in situ generation of vinylidene and alkylidene complexes based on the activation of alkynes with transition metal compounds was investigated. The cyclic oxacarbene complexes are produced through the formation of vinylidene complexes followed by the electrocyclization with the neighboring subunit of an alkyne. During the course of the study, it was found that a transition metal-induced 5-exo-dig cyclization of alkynes having nucleophilic conjugate subunits affords new types of hetero arene-substituted carbene complexes, such as (2-furyl)-, (2-pyrroryl), and (2-thienyl)carbene complexes. The 5-exo-dig cyclization of propargyl esters followed by 1,2-migration of carboxylates leads to the formation of vinylcarbene complexes. The in situ generation of metal-carbenoid species is highly atom-efficient and widely applicable to organic syntheses. In this account, the in situ generation of carbenoid species from a range of alkynes and synthetic applications to catalytic carbene transfer reactions, such as cycloaddition, annulation, ylide-associated reactions, insertion reactions, cycloisomerization, and isomerization reactions are highlighted and reviewed. Scheme 1. Slippage of ML n in nucleophilc attack to the bound alkyne.Scheme 2. Generation of carbene complexes via cyclization of carbonyl-ene-yne compounds.Scheme 3. Generation of vinylcarbene complexes from propargyl esters. Cyclic Carbene Complexes from Conjugated AlkynesWe reported rhodium-catalyzed cycloaromatization of conjugated acyclic enediynes on the basis of the in situ generation of vinylidene-metal followed by Saito-Myers type cyclization leading to radical species (Scheme 4). 12 In the course of our study on the in situ generation of vinylidene complexes in other conjugate systems, we focused our attention on an electrocyclization of vinylidene complexes generated from conjugated alkynes having carbonyl subunits. The first attempt to obtain a benzopyranylidene from an alkyne-conjugated ester or amide 1a,b with M(CO) 5 (THF) (M = group 6 metals) was unsuccessful (Scheme 5). The formation of a benzopyranylidene complex having an alkoxy or an amino group appeared to be insufficient to compensate for the loss of aromaticity due to the ortho quinonoid structure. Replacement of an aromatic unsaturated juncture with an aliphatic C=C bond led us to find a new 6-endo-dig cyclization based on the in situ generation of a vinylidene complex. Ester or amide derivatives 2a,b produced the yellow crystalline pyranylidene complexes 3a,b as a cyclic Fischer-type oxacarbene complex (Scheme 6).13,14a The selected NMR data are summarized in Table 1. The structure of tungsten-complex, 3a-W was unambiguously determined by X-ray crystallography (Figure 1). Independently, Iwasawa and co-workers reported the interesting benzopyranylidene complexes obtained from keto analogue of 1c (Scheme 7a). 15They also demonstrated the formation of interesting carbenoid-containing carbonyl ylides (tungsten-containing benzopyryliums) generated from 1c in the presence of reactants (...

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Section: Cyclic Carbene Complexes From Conjugated Alkynesmentioning

confidence: 99%

“…16 The dichotomous behavior of the alkyne complex is explained by the rapid equilibrium between an alkyne complex and a carbenoid-containing carbonyl ylide generated via 6-endo-dig cyclization, and the irreversible formation of benzopyranylidene complexes generated via a vinylidene complex.…”

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confidence: 99%

Development of Catalytic Carbene Transfer Reactions Using Alkynes as a Source of Carbenes

Ohe

Miki

2009

J. Synth. Org. Chem. Jpn.

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“…As part of our continuous efforts to develop safe and practical carbene chemistry based on enynals/enynones as efficient carbene precursors, [7,8] we report herein the first enantioselective intramolecular C À H insertion and cyclopropanation reactions of donor-and donor/donor-carbenes by a nondiazo approach. As dihydroindole and dihydrobenzofuran are core structures of a variety of natural and bioactive compounds, our first target was to explore CÀH insertion reactions of donor/donor-metal carbenoids, which are gen-…”

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confidence: 99%

Enantioselective Intramolecular C−H Insertion of Donor and Donor/Donor Carbenes by a Nondiazo Approach

et al. 2016

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“…It is well known that metal carbenoids [6] can be generated from alkynes in the following three ways (Scheme 1): 1) nucleophilic attack of an alkyne activated by metals and subsequent trapping of the vinyl-metal species by an electrophile; [7] 2) attack of the activated alkyne by a nucleophile bearing a leaving group (LG), thereby generating a-oxo-, a-imino-, or a-vinyl-metal carbenoids; [8] 3) the use of an uncharged element containing a lone pair of electrons as the nucleophile, which provides aylide-type metal carbenoids. [9] The first two modes are very common in the literature, but, the third is relatively rare.…”

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confidence: 99%

Catalyst‐Dependent Divergent Synthesis of Pyrroles from 3‐Alkynyl Imine Derivatives: A Noncarbonylative and Carbonylative Approach

et al. 2014

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Generation and Reaction of Metal-Containing Carbonyl Ylides: Tandem [3+2]-Cycloaddition−Carbene Insertion Leading to Novel Polycyclic Compounds

Cited by 153 publications

References 5 publications

Development of Catalytic Carbene Transfer Reactions Using Alkynes as a Source of Carbenes

Development of Catalytic Carbene Transfer Reactions Using Alkynes as a Source of Carbenes

Enantioselective Intramolecular C−H Insertion of Donor and Donor/Donor Carbenes by a Nondiazo Approach

Catalyst‐Dependent Divergent Synthesis of Pyrroles from 3‐Alkynyl Imine Derivatives: A Noncarbonylative and Carbonylative Approach

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