The Reactivity of Complexes of Nickel(0) and Platinum(0) Containing Benzyne and Related Small‐Ring Alkynes

Abstract

The preparation and reactivities of cyclohexyne and aryne complexes of platinum@) and nickel(0) are reviewed. These complexes undergo insertions with unsaturated molecules such as alkenes, alkynes, isocyanides, CO and C 0 2 . I n the case of the nickel-benzyne complexes, consecutive insertions are observed with alkynes, leading to substituted naphthalenes with good regioselectivities. A possible mechanism for these double insertions, based on a combination of steric and electronic factors, is discussed in detail.

Palladium-Catalyzed Cycloaddition Reactions of Arynes

“…Although further investigation is needed to determine these mechanisms in detail, a pathway similar to the one generally accepted for alkyne cyclotrimerization is consistent with reports on the reactivity of aryne complexes of group 10 elements [66].…”

Ab initio molecular orbital study of conformational properties of cyclohexyne, cycloheptyne, and cyclooctyne

“…Most synthetic chemists appear still to consider cyclohexyne and its derivatives to be chemical curiosities 17, 18. Concerning the six‐membered ring cycloalkynes, a great number of cyclohexyne derivatives have been reported 19.…”

Chemodivergent Nickel(0)-Catalyzed Arene C–F Activation with Alkynes: Unprecedented C–F/C–H Double Insertion

“…Furthermore, the use of the 8-aminoquinoline group allowed us to isolate an unprecedented organometallic nickel(II) metalacycle featuring a doubly inserted acetylene, as the key intermediate in the aromatic homologation strategy (Scheme 1c). 43 Scheme 1. (a) Nickel-catalyzed C-F activation reactions using highly reactive, preactivated R-M nucleophiles.…”