Table 1. Effect of selected parameters on the arylation of Boc-1,3-oxazinanes.

Entry	Z	Reactant	Diamine	Ligand	8/9a	Product	Yield (%)b	e.r.c
1d	Me	7a	TMEDA	L3	>98:2	8aa	54	–
2d	Me	7a	(+)-sp	L3	>98:2	8aa	53	75:25
3d	Et	7b	(+)-sp	L3	>98:2	8ab	51	95:5
4d	Et	7b	(+)-sp surrogate	L3	>98:2	8ab	46	91:9
5d	n-Pr	7c	(+)-sp	L3	>98:2	8ac	30	94:6
6e,f	Et	7b	(+)-sp	L3	>98:2	8ab	61	97:3
7a	Me	7a	TMEDA	L2	<2:98	9aa	65	–
8	Me	7a	(+)-sp	L2	<2:98	9aa	51	77.5:22.5
9	Et	7b	(+)-sp	L2	<2:98	9ab	48	97:3
10	Et	7b	(+)-sp surrogate	L2	<2:98	9ab	89	94:6
11f	n-Pr	7c	(+)-sp	L2	<2:98	9ac	72	96.5:3.5
12	–(CH2)4–	7d	(+)-sp	L2	<2:98	9ad	23	85:15

Reaction conditions unless otherwise stated: 7 (1.0 equiv), s-BuLi (1.2 equiv), diamine (1.2 equiv), Et₂O, –78 °C, 8 h, then ZnCl₂/THF (1.2 equiv), –78→20 °C, 1 h, then removal of volatiles, then PhBr (0.7 equiv), Pd₂dba₃ (2.5 mol%), ligand (5 mol%), toluene, 80 °C, 17-24 h.

^aMeasured by GCMS or ¹H NMR analysis of the crude reaction mixture.

^bYield of the isolated product.

^cDetermined by HPLC on a chiral stationary phase.

^dCross-coupling step performed at 60 °C instead of 80 °C.

^eUsing Zn(OAc)₂ instead of ZnCl₂ and PhONf instead of PhBr.

^fConditions employed in Fig. 3-4. Nf = SO₂(CF₂)₃CF₃.