Catalytic Isonitrile Insertions and Condensations Initiated by RNC–X Complexation

Chakrabarty, Suravi; Choudhary, Sonal; Doshi, Arpit; Liu, Faqiang; Mohan, Rosmin Elsa; Ravindra, Manasa; Shah, Dhruv; Yang, X.-M.; Fleming, Fraser F.

doi:10.1002/adsc.201400017

Cited by 129 publications

(53 citation statements)

References 221 publications

(317 reference statements)

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“…Sulfonylmethyl isonitriles such as TosMIC [(tolylsulfonyl)methyl isocyanide; Scheme 1; compound 3 , R 1 = p Tol], are extremely valuable precursors to multifarious isonitriles, [1] heterocycles, [2] and N-heterocyclic carbene complexes. [3] Traditionally, metal sulfinates 1 have featured prominently in the stoichiometric [4] and metal-catalyzed [5] syntheses of sulfonylmethyl isonitriles and sulfones.…”

Section: Introductionmentioning

confidence: 99%

Alkyl Sulfinates: Formal Nucleophiles for Synthesizing TosMIC Analogs

2015

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Alkyl sulfinates function as formal nucleophiles in Mannich-type reactions to give sulfonyl formamides, which are readily dehydrated to the corresponding sulfonylmethyl isonitriles. The efficient, two-step synthesis provides a general route to sulfonylmethyl isonitriles from readily available methyl sulfinates or thiols. Mechanistic analysis reveals that the unusual nucleophlicity of the alkyl sulfinates arises from the in situ release of sulfinic acids.

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Section: Introductionmentioning

confidence: 99%

Alkyl Sulfinates: Formal Nucleophiles for Synthesizing TosMIC Analogs

2015

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“…[1] The carbene-like structure (Figure 1) [2] confers ambiphilic reactivity on the isocyanide carbon that manifests an exceptionally diverse reactivity for one functional group: metal insertion, [3] radical additions, [4] nucleophilic additions, [1] and electrophilic alkylations. [5] The high reactivity toward disparate reagents is particularly valuable for multicomponent reactions, [5] heterocycle synthesis, [6] and accessing acyclic nitrogenous scaffolds.…”

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Alkenyl Isocyanide Conjugate Additions: A Rapid Route to γ‐Carbolines

et al. 2017

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Isocyanides are exceptional building blocks whose wide deployment in multi-component and metal insertion reactions belies their limited availability. Addressing this deficiency is the first conjugate addition-alkylation method. An array of organolithiums, magnesiates, enolates, and metalated nitriles, add conjugately to β- and β, β-disubstituted arylsulfonyl alkenyl isocyanides to rapidly assemble diverse isocyanide scaffolds. The intermediate metalated isocyanides are efficiently trapped with electrophiles to generate substituted isocyanides incorporating contiguous tri- and tetra-substituted centers. The substituted isocyanides are ideally functionalized for elaboration into synthetic targets as illustrated by the three-step synthesis of the γ-carboline, N-methyl ingenine B.

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“…[21] Complexation of copper [22] likely activates the alkeneisocyanide for cycloaddition ( 6 → 12 ) to afford 13 . A 1,3-H shift in 13 restores the aromaticity which primes 14 for two sequential copper-assisted decyanations.…”

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Direct Conversion of Nitriles into Alkene “Isonitriles”

Fleming

2016

Angew Chem Int Ed

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The sequenced addition of RLi to nitriles, trapping with isopropylformate, and dehydration with phosphoryl chloride provides an efficient, direct synthesis of alkeneisocyanides. The one-pot sequence involves a series of carefully orchestrated steps: addition, formylation, tautomerization, and dehydration, with CuCN catalyzing a key equilibration of a formyl imine to an N-formyl enamine. The resulting aromatic alkeneisocyanides, that are otherwise challenging to synthesize, engage in an unusual [4+2] type cycloaddition-1,3-H shift-decyanation sequence to afford substituted naphthalenes.

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Catalytic Isonitrile Insertions and Condensations Initiated by RNC–X Complexation

Cited by 129 publications

References 221 publications

Alkyl Sulfinates: Formal Nucleophiles for Synthesizing TosMIC Analogs

Alkyl Sulfinates: Formal Nucleophiles for Synthesizing TosMIC Analogs

Alkenyl Isocyanide Conjugate Additions: A Rapid Route to γ‐Carbolines

Direct Conversion of Nitriles into Alkene “Isonitriles”

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