Dawn of organopalladium chemistry in the early 1960s and a retrospective overview of the research on palladium-catalyzed reactions

Enantioselective α‐Benzylation of Acyclic Esters Using π‐Extended Electrophiles

“…[1] Under the action of a suitable Pd catalyst, carbogenic nucleophiles react efficiently with allylic electrophiles. These reactions typically proceed via cationic π-(allyl)Pd II L n species, the reactivity and stereocontrol elements of which can be readily tuned by the supporting ligands.…”

Palladium‐Catalyzed Asymmetric C(sp3)−H Allylation of 2‐Alkylpyridines

“…[1] Among methods used to access these structures, [2] the asymmetric Tsuji-Trost allylation reactions with 2-alkylazaarenes as pronucleophiles allow enantioselective C(sp 3 )À C(sp 3 )bond formation at the position a to the azaarene ring, and is ap romising strategy. [1] Among methods used to access these structures, [2] the asymmetric Tsuji-Trost allylation reactions with 2-alkylazaarenes as pronucleophiles allow enantioselective C(sp 3 )À C(sp 3 )bond formation at the position a to the azaarene ring, and is ap romising strategy.…”

“…Specifically, P(2-furyl) 3 and P(OPh) 3 led to moderate substrate conversion to give the linear allylation product 3a preferentially over the branched product 3a' ' (3a/3a' ' 93:7 and 97:3, respectively). Specifically, P(2-furyl) 3 and P(OPh) 3 led to moderate substrate conversion to give the linear allylation product 3a preferentially over the branched product 3a' ' (3a/3a' ' 93:7 and 97:3, respectively).…”

“…Azaarenes with an a-stereogenic alkyl substituent at the C2position constitute an important structural motif widely found in biologically active compounds,a grochemicals,a nd natural products. [1] Among methods used to access these structures, [2] the asymmetric Tsuji-Trost allylation reactions with 2-alkylazaarenes as pronucleophiles allow enantioselective C(sp 3 )À C(sp 3 )bond formation at the position a to the azaarene ring, and is ap romising strategy. [3] However,r eported methods have required the use of either stoichiometric or excess amounts of strong Brønsted bases and/or Lewis acids to activate the C(sp 3 )ÀHbonds of the pronucleophiles (Scheme 1a).…”

“…[1] Among methods used to access these structures, [2] the asymmetric Tsuji-Trost allylation reactions with 2-alkylazaarenes as pronucleophiles allow enantioselective C(sp 3 )À C(sp 3 )bond formation at the position a to the azaarene ring, and is ap romising strategy. [3] However,r eported methods have required the use of either stoichiometric or excess amounts of strong Brønsted bases and/or Lewis acids to activate the C(sp 3 )ÀHbonds of the pronucleophiles (Scheme 1a). [4][5][6] This report describes the palladium-catalyzed asymmetric C(sp 3 ) À Ha llylation of 2-alkylpyridines with primary allylic carbonates,and it does not require the use of an external base.…”