Ruthenium‐Catalyzed Oxidative Cross‐Coupling of Alkenes with Triisopropylsilylacetylene

Abstract

A Ruthenium-catalyzed 2-pyridyl or 2-pyrimidyl directed oxidative cross-coupling reaction of alkenes with triisopropylsilylacetylene was carried out. This protocol suits for mono-, di-and trisubstituted ethenes, as well as various (substituted pyridyl)alkenes and exhibits good compatibility of functional groups and Z-selectivity of the enyne products.

Recent Advances in Alkenyl sp2 C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

“…Gratifyingly, both 2-pyridyl and 2pyrimidyl were competent directing groups for this strategy, enabling the synthesis of highly functionalized 3-enyne products in good yields with excellent Z-selectivity (Scheme 274). 445…”

Density Functional Theory Study on the Mechanism of Nickel-Catalyzed 3,3-Dialkynylation of 2-Aryl Acrylamides Via Double Vinylic C–H Bond Activation

“…Olefinic C­(sp 2 )–H alkynylation has been an active area of research in the past decade for the flexibility of introducing complex groups and constructing novel compounds. − In the past decades, much progress has been achieved in the direct olefinic C­(sp 2 )–H alkynylation using noble transition metals such as Pd, − Rh, − Ru, and Au, and the participation of chelation-assisted systems with N , N -bidentate directing groups has been an ideal approach to achieve site-selective C–H bond functionalization. − Recently, the development of direct C–H alkynylation catalyzed by 3d transition metals to construct C­(sp 2 )–C­(sp) bonds has been a promising direction because of their low price and lower toxicity. For instance, in 2015, Yi et al reported a nickel-catalyzed C–H alkynylation reaction between two kinds of inactivated C­(sp 2 )–H and triisopropylsilyl (TIPS)-substituted bromoalkyne, which is the first report on Ni-catalyzed C­(sp 2 )–C­(sp) bond formation via 8-quinolinyl-chelation assistance .…”