A one-step diastereoselective synthesis of bulky P-chiral phosphines with a rigid bicyclic [2.2.1] structure was developed employing a cycloaddition reaction of 3,4,5-triphenyl-1-(+)-neomenthyl-1,2-diphosphole (1) and maleic acid derivatives. The catalytic activity and asymmetric induction for the prepared enantiopure tricyclic phosphines 2a and 3a were evaluated in Pd-catalyzed asymmetric allylic substitution and [3 + 2] organocatalytic cyclization of allenes with activated alkenes (ee = 68%). This is the first example of using a chiral phosphine with a P-P bond as ligand in allylic alkylation and organocatalyst in a [3 + 2] annulation. (C) 2016 Elsevier B.V. All rights reserved.