Recent Progress in Nonclassical Isocyanide‐Based MCRs

Ramón, Rosario; Kielland, Nicola; Lavilla, Rodolfo

doi:10.1002/9783527652532.ch9

Cited by 4 publications

(1 citation statement)

References 129 publications

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“…Isocyanides (C≡NR) are highly demanding reagents toward materials with valuable properties [ 1 , 2 , 3 ] and they have a broad application in multicomponent [ 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 ] and insertion [ 4 , 13 , 14 , 15 , 16 , 17 , 18 ] reactions, catalysis [ 4 , 13 , 14 , 19 , 20 , 21 , 22 ], and polymer chemistry [ 15 ]. One of the most important types of the reactivity involving isocyanides is nucleophilic addition (NA) at the carbon atom of the C≡N group ( Scheme 1 ).…”

Section: Introductionmentioning

confidence: 99%

Metal-Mediated Addition of N-Nucleophiles to Isocyanides: Mechanistic Aspects

Kuznetsov

Kukushkin

2017

Molecules

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Despite the long history of the investigation of nucleophilic addition to metal-bound isocyanides, some important aspects of the reaction mechanism remain unclear even for the simplest systems. In this work, the addition of the sp3-N, sp2-N, and mixed sp2/sp3-N nucleophiles (i.e., HNMe2, HN=CPh2, and H2N–N=CPh2, respectively) to isocyanides C≡NR coordinated to the platinum(II) centers in the complexes cis-[Pt(C≡NCy)(2-pyz)(dppe)]+ (2-pyz = 2-pyrazyl, dmpe = Me2PCH2CH2PMe2) and cis-[PtCl2(C≡NXyl)(C≡NMe)] was studied in detail by theoretical (DFT) methods. The mechanism of these reactions is stepwise associative rather than concerted and it includes the addition of a nucleophile to the isocyanide C atom, deprotonation of the nucleophilic moiety in the resulting intermediate, and protonation of the isocyanide N atom to give the final product. The calculated activation energy (ΔG≠) of all reactions is in the range of 19.8–22.4 kcal/mol.

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Section: Introductionmentioning

confidence: 99%

Metal-Mediated Addition of N-Nucleophiles to Isocyanides: Mechanistic Aspects

Kuznetsov

Kukushkin

2017

Molecules

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Functionalization of Heterocycles by MCRs

Vicente‐García

Kielland

Lavilla

2014

Multicomponent Reactions in Organic Synthesis

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Silver‐Promoted [3+1+1] Annulation of Isocyanoacetates with Nitrosoarenes

et al. 2018

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3+ +1+ +1] annulation of isocyanoacetates with nitrosoarenes for the preparation of 1,4,5-trisubstituted imidazoles or 4,5-dihydro-1H-imidazoles has been disclosed. Isocyanoacetates serve as both at hree-atom component and ao ne-carbonu nit in the reaction. Specially, with catalytic amounts of Ag 2 CO 3 and ar educed temperature this [3+ +1+ +1] annulation of isocyanoacetates enablest he formation of trans-imidazolines in good yield and with high diastereoselectivity.S ilver plays ac ritical dual role:i )ast he catalyst for the efficiency to activate the isocyanides and ii)the oxidantina romatization process.

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Recent Progress in Nonclassical Isocyanide‐Based MCRs

Cited by 4 publications

References 129 publications

Metal-Mediated Addition of N-Nucleophiles to Isocyanides: Mechanistic Aspects

Metal-Mediated Addition of N-Nucleophiles to Isocyanides: Mechanistic Aspects

Functionalization of Heterocycles by MCRs

Silver‐Promoted [3+1+1] Annulation of Isocyanoacetates with Nitrosoarenes

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