Selective cyclization and substitution was achieved with designated 1,2,3-triazole acid auxiliary groups under Pd catalyzed C-H activation conditions. Both sp 2 and sp 3 C-H bonds were effectively activated,

In this paper, the air-stable and readily available 1,3,5-triaza-7-phosphaadmantane (PTA) is reported as a practical and versatile nucleophilic phosphine organocatalyst. Under the mediation of 15-30 mol % of PTA, various electrophiles like aldehydes and imines readily undergo the MoritaBaylis-Hillman reactions with a variety of activated olefins, giving the corresponding adducts in high yields. In the phosphine-catalyzed [3 + 2] cycloaddition reaction of 4-substituted 2,3-butadienoates with N-tosylimines, PTA is also proven to be a comparable catalyst as tributylphosphine (PBu 3 ). By systematic comparison with other structurally similar N,P catalysts, it is concluded that the superiority of PTA in the above nucleophilic catalysis is attributable to its comparable nucleophilicity with that of trialkylphosphines. The feasibility to use PTA as an alternative catalyst in place of the air-sensitive trialkylphosphines is also discussed.

1,3,5,-Triaza-7-phosphaadamantane (PTA) is first reported to be a convenient and efficient nucleophilic trialkylphosphine organocatalyst for the Baylis-Hillman reaction. Thus, under the mediation of 15 -20 mol % of PTA and practical conditions, both aromatic and aliphatic aldehydes react with the activated alkenes like acrylates and methyl vinyl ketone to afford the corresponding adducts in fair to excellent yields.