Selected optimisation of the Pd-AAA reactions of cyclic imine 2a with allyl carbonate 1a with chiral bidentate phosphine ligands^a.

Entry	Ligand	Solvent	Yieldb (%)		erc
			3aa	4aa
1d	L1	THF	90	—	93 : 7
2	L2	THF	NR		—
3	L3	THF	NR		—
4	L4	THF	73	6	83 : 17
5	L5	THF	97	—	91 : 9
6 e	L1	CH 2 Cl 2	90	—	91 : 9
7	L2	CH2Cl2	17	10	84 : 16
8	L3	CH2Cl2	6	9	62 : 38
9	L4	CH2Cl2	54	6	85 : 15
10	L5	CH2Cl2	7	—	35 : 65f
11e,g	L1	CH2Cl2	78	—	91 : 9
12e,h	L1	CH2Cl2	86	—	91 : 9
13e,i	L1	CH2Cl2	84	—	92 : 8
14e,j	L1	CH2Cl2	85	—	93 : 7
15e,k	L1	CH2Cl2	61	—	91 : 9

^aReaction conditions: 1a (0.2 mmol, 1.0 equiv.), 2a (0.22 mmol, 1.1 equiv.), [Pd(π-C₃H₅)Cl]₂ (5 mol%), L (15 mol%), solvent (0.07 M w r t. 1a), rt, 21 h.

^bYield determined by ¹H NMR integration against an internal standard (dimethyl sulfone or trans-stilbene oxide).

^cEnantiomeric ratio determined by chiral HPLC.

^dReaction reached completion after 3 h.

^eReaction reached completion after 1 h.

^fReversed enantioselectivity compared to entry 5.

^g[Pd(π-C₃H₅)Cl]₂ (2.5 mol%), L (7.5 mol%).

^hReaction concentration halved (0.04 M w. r. t. 1a).

ⁱ i-1a (1.0 equiv.) used instead of 1a.

^jPd₂dba₃·CHCl₃ (5 mol%).

^k 4aa was employed as SM.