Copper(II) Triflate Catalyzed Intermolecular Aromatic Substitution of <i>N</i>,<i>N</i>‐Disubstituted Anilines with Diazo Esters

Tayama, Eiji; Yanaki, Tomoyo; Iwamoto, Hajime; Hasegawa, Eietsu

doi:10.1002/ejoc.201001083

Cited by 52 publications

(24 citation statements)

References 10 publications

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“…This result clearly indicated an orthogonal reactivity of the gold catalyst compared to a dirhodium catalyst, which exclusively promoted the benzylic CÀH insertion without the occurrence of electrophilic aromatic substitution. [12] Scheme 1. Reactivity of gold-carbenoids: carbene versus carbocation.…”

mentioning

confidence: 99%

Chemoselective Carbophilic Addition of α‐Diazoesters through Ligand‐Controlled Gold Catalysis

et al. 2014

Angew Chem Int Ed

260

113

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The chemoselective addition of arenes and 1,3-diketones to α-aryldiazoesters was achieved through ligand-controlled gold catalysis. Unlike a dirhodium catalyst (which promotes C(sp3)-H insertion and cyclopropanation) and a copper catalyst (which catalyzes O-H and N-H insertions), the gold catalyst with an electron-deficient phosphite as the ancillary ligand exclusively gave the carbophilic addition product, thus representing a new and efficient approach to form "carbophilic carbocations", which selectively react with carbon nucleophiles.

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confidence: 99%

Chemoselective Carbophilic Addition of α‐Diazoesters through Ligand‐Controlled Gold Catalysis

et al. 2014

Angew Chem Int Ed

260

113

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“…Indeed, it was observed that a reaction involving indole, N-methylaniline, and 1a resulted in the unsymmetrical diaryl product 7, albeit in low yield. We investigated a few additional precursors and found that, while N-methylaniline and indoline afforded diarylated products in low yields (compounds 7,8,and 9;Scheme 2a),. Employing pyrrole in place of indole also did not lead to the desired product, indicating another limitation of this protocol.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…9 It was found that free anilines reacted via the para position to afford the unsymmetrical diarylacetates in generally high yields (52−86%). 10 Gratifyingly, N-benzylaniline provided the product in good yield, thereby overcoming the limitation of the direct protocol in Scheme 2.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis of Unsymmetrical α,α-Diarylacetates

Jadhav

Singh

2015

J. Org. Chem.

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Ethyl bromofluoroacetate has been developed as a precursor for the convenient synthesis of unsymmetrical α,α-diarylacetates featuring indoles, anilines, and other electron-rich aromatics. In conjunction with a mild Lewis acid catalyzed C-N → C-C exchange, intermediate arylglycines can be synthesized and transformed into α,α-diarylacetates in a one-pot protocol, resulting in a net diarylation reaction exhibiting a wide scope. In the context of diarylacetates, the synthetic equivalence of the fluorinated reagent with α-nitro-α-diazo carbonyls was established.

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“…The groups of Fox [4] and Wang [5] have reported ortho-selective C À H functionalization of heterocycles by using diazoacetates. In addition, other directing groups, such as purines, [6] azacycles, [7] disubstituted anilines, [8] and phenols, [9] have been utilized in metallocarbene CÀH alkylation reactions. Collectively, these directing groups limit the synthetic applicability of metallocarbene C À H alkylation reactions.Recently, Suero and co-workers reported the synthesis of aryl diazoacetate derivatives under photoredox conditions.…”

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Regioselective Arene C−H Alkylation Enabled by Organic Photoredox Catalysis

2020

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Expanding the toolbox of C À H functionalization reactions applicable to the late-stage modification of complex molecules is of interest in medicinal chemistry, wherein the preparation of structural variants of known pharmacophores is a key strategy for drug development. One manifold for the functionalization of aromatic molecules utilizes diazo compounds and a transition-metal catalyst to generate a metallocarbene species, which is capable of direct insertion into an aromatic CÀH bond. However, these high-energy intermediates can often require directing groups or a large excess of substrate to achieve efficient and selective reactivity. Herein, we report that arene cation radicals generated by organic photoredox catalysis engage in formal C À H functionalization reactions with diazoacetate derivatives, furnishing sp 2 -sp 3 coupled products with moderate-to-good regioselectivity. In contrast to previous methods utilizing metallocarbene intermediates, this transformation does not proceed via a carbene intermediate, nor does it require the presence of a transitionmetal catalyst.Metallocarbenes are reactive organometallic species that may be generated by using a transition-metal precursor and diazoacetate derivatives. [1][2][3] The resulting carbene intermediate may then undergo CÀH insertion with reactive CÀH bonds (often aryl or alkyl), affording the corresponding alkylated adducts. However, owing to the high reactivity of metallocarbenes, aromatic substrates are often required to be present in excess for efficient reactivity.Among methodologies based on metallocarbene CÀH insertion that do not use a several-fold excess of arene, directing groups are often required. The groups of Fox [4] and Wang [5] have reported ortho-selective C À H functionalization of heterocycles by using diazoacetates. In addition, other directing groups, such as purines, [6] azacycles, [7] disubstituted anilines, [8] and phenols, [9] have been utilized in metallocarbene CÀH alkylation reactions. Collectively, these directing groups limit the synthetic applicability of metallocarbene C À H alkylation reactions.Recently, Suero and co-workers reported the synthesis of aryl diazoacetate derivatives under photoredox conditions. [10]

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Copper(II) Triflate Catalyzed Intermolecular Aromatic Substitution of N,N‐Disubstituted Anilines with Diazo Esters

Cited by 52 publications

References 10 publications

Chemoselective Carbophilic Addition of α‐Diazoesters through Ligand‐Controlled Gold Catalysis

Chemoselective Carbophilic Addition of α‐Diazoesters through Ligand‐Controlled Gold Catalysis

Synthesis of Unsymmetrical α,α-Diarylacetates

Regioselective Arene C−H Alkylation Enabled by Organic Photoredox Catalysis

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