Palladium-Catalyzed Cleavage Reaction of Carbon−Carbon Triple Bond with Molecular Oxygen Promoted by Lewis Acid

Abstract

A new Lewis acid promoted and palladium-catalyzed cleavage reaction of carbon-carbon triple bond with molecular oxygen was reported, in which alkyne or 1.3-diynes is split into carboxylic ester in various alcohols.

Silver‐Catalyzed Nitrogenation of Alkynes: A Direct Approach to Nitriles through CC Bond Cleavage

“…[7] Furthermore, the coupling of terminal alkynes, such as the Sonogashira coupling (Scheme 1 e), provides important methods for CÀC bond formation. [8] The catalytic cleavage of CC bonds to produce carboxylic acids [9] and new alkynes [10] has also been disclosed (Scheme 1 f,g). Because of the significance and wide applications of such chemistry in organic synthesis, the exploration for new types of alkyne transformations is very attractive to researchers.…”

“…[12][13][14][15] Azides have been widely used in organic reactions, [16][17][18] but recent progress on the direct transformation of simple hydrocarbons into N-containing compounds [18] through a nitrogenation strategy encouraged us to try the direct transformation of alkynes. Although metal-catalyzed C C bond cleavage involving alkyne metathesis has been disclosed, [9,10] direct CC bond cleavage to form nitriles (Scheme 1 h) is still unknown and remains both challenging and of great value.…”

Scandium triflate catalyzed unexpected cleavage of C-C bonds in ynones

“…Extensive literature study reveals that there exist quite a few reports catalytic cleavage of C(sp)-C(sp) bonds of unactivated alkynes. [19][20][21][22][23][24] However, such kind of C(sp)-C(sp) bond cleavage in ynones are remains uncommon 25 . Similarly, it should be noted that the such kind of cleavage in 1,3-diketone 26,27 has literature precedence; however, the use of naked H + , [28][29][30][31][32] amines 33 or strong bases [34][35] are necessary and the reactions are low yielding.…”

Palladium/copper tandem catalysis for carbon–carbon triple bond cleavage of diaryl acetylenes

“…7 However, other transformations that relied on the catalytic cleavage of the carbon-carbon triple bond still remain in a few examples. [8][9][10][11] As a result, research on developing new methods for C"C bond cleavage will no doubt enrich the potential application of alkyne in organic synthesis.…”

“…The transformation afforded products with para-, meta-, ortho-methyl substituents in moderate yields ( Table 2, entries 2 -5). Substrates with the halo group, such as fluoro, chloro, and bromo, were well-tolerated, giving the corresponding amides in moderate to good yields (entries [7][8][9][10][11][12]. Notably, substrates with trifluoromethyl and cyano were also compatible (entries 13 and 14).…”