NHC-Ni(II)-catalyzed cyclopropene-isocyanide [5 + 1] benzannulation

Isocyanides are common compounds in fine and bulk chemical syntheses. However, the direct addition of isocyanide to simple unactivated cyclopropene via transition metal catalysis is challenging. Most of the current approaches focus on 1,1-insertion of isocyanide to M-R or nucleophilc insertion. That...

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Bibliographic Details
Published in:Nature communications 2022-07, Vol.13 (1), p.4145-4145, Article 4145
Main Authors: Huang, Jian–Qiang, Yu, Meng, Yong, Xuefeng, Ho, Chun–Yu
Format: Article
Language:English
Subjects:
639/638/403/933
639/638/549/933
639/638/77/888
Aniline
Carbenes
Catalysis
Catalysts
Cross-reactivity
Crystal structure
Humanities and Social Sciences
Hydroquinone
Insertion
Ligands
multidisciplinary
Nickel
Oligomerization
Organic compounds
Polymerization
Reactivity
Ring structures
Room temperature
Science
Science (multidisciplinary)
Substitutes
Substrates
Transition metals
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Summary:Isocyanides are common compounds in fine and bulk chemical syntheses. However, the direct addition of isocyanide to simple unactivated cyclopropene via transition metal catalysis is challenging. Most of the current approaches focus on 1,1-insertion of isocyanide to M-R or nucleophilc insertion. That is often complicated by the competitive homo-oligomerization reactivity occurring at room temperature, such as isocyanide 1,1-insertion by Ni(II). Here we show a (N-heterocyclic carbene)Ni(II) catalyst that enables cyclopropene-isocyanide [5 + 1] benzannulation. As shown in the broad substrate scope and a [ trans- (N-heterocyclic carbene)Ni(isocyanide)Br 2 ] crystal structure, the desired cross-reactivity is cooperatively controlled by the high reactivity of the cyclopropene, the sterically bulky N-heterocyclic carbene, and the strong coordination ability of the isocyanide. This direct addition strategy offers aromatic amine derivatives and complements the Dötz benzannulation and Semmelhack/Wulff 1,4-hydroquinone synthesis. Several sterically bulky, fused, and multi-substituted anilines and unsymmetric functionalized spiro-ring structures are prepared from those easily accessible starting materials expediently. The direct addition of isocyanides to cyclopropenes is challenging. Here, the authors report a catalytic cyclopropene-isocyanide [5 + 1] benzannulation catalyzed by an (N-heterocyclic carbene)Ni(II) complex; this method enables the preparation of fused and multi-substituted anilines and unsymmetrically functionalized spiro-ring structures.
ISSN:2041-1723
2041-1723
DOI:10.1038/s41467-022-31896-y