Table 3.

Substrate scope of intermolecular chloroetherification.

Entry	Starting material	R1	R2	Product	Yield [%][a]	d.r.	r.r.[b]	e.r.[c]
1	E-1b-NO2	Ph	H	a-2b-OMe-NO2[e]	56 (49)[d]	3.4:1	>99:1	92:8
2	E-1d-NO2	pF-Ph	H	a-2d-OMe NO2[e]	64 (58)[d]	3.3:1	>99:1	90:10
3	E-1c-NO2	n-C3H7	H	a-2c-OMe NO2	86 (79)	>99:1	>20:1	87:13
4	E-1a-NO2	CyHex	H	a-2a-OMe NO2	70	>99:1	>20:1	75:25
5	E-1e-NO2	BnOCH2	H	a-2e-OMe-NO2	62 (57)	>99:1	7:1	89:11
6	Z-1b-NO2	H	Ph	s-2b-OMe-NO2	93 (82)[d]	3.3:1	>99:1	99.5:0.5 (90:10)[f]
7	Z-1f-NO2	H	pMe-Ph	s-2f-OMe-NO2	87[d]	1.3:1	>99:1	98:2 (97:3)[f]
8	Z-1g-NO2	H	pMeO-Ph	s-2g-OMe-NO2	80[d]	1:1	>99:1	99:1 (92:8)[f]
9	Z-1h-NO2	H	C2H5	s-2h-OMe-NO2	83 (77)	>99:1	>20:1	98:2
10	Z-1c-NO2	H	C3H7	s-2c-OMe-NO2	87 (79)g	>99:1	>20:1	99.5:0.5 (99.5:0.5)[g]
11	Z-1i-NO2	H	C5H11	s-2i-OMe-NO2	83 (74)	>99:1	>20:1	95:5
12	Z-1e-NO2	H	BnOCH2	s-2e-OMe-NO2	60 (53)	>99:1	7:1	99.5:0.5
13	Z-1j-NO2	H	TBDPSOC2H4	s-2j-OMe-NO2	79	>99:1	>20:1	99.5:0.5
14	1k-NO2	Me	Me	2k-OMe-NO2	59 (53)	na	na	99:1
15[h]	E-1b-NO2	Ph	H	ent-a-2b-OMe-NO2[e]	42[d]	6.2:1	>99:1	75:25
16[h]	Z-1f-NO2	H	pMe-Ph	ent-s-2f-OMe-NO2	82	1.2:1	>99:1	99.5:0.5 (96:4)[f]
17[h]	Z-1c-NO2	H	C3H7	ent-s-2c-OMe-NO2	69	>99:1	>20:1	95:5

^[a]Yield determined by NMR with MTBE as standard. Numbers in parentheses reflect yields of isolated product on a 0.1 mmol scale.

^[b]r.r. (regioselectivity) is defined as ratio of 2:5, see Table 4.

^[c]Enantioselectivity determined by chiral-phase HPLC.

^[d]Combined yield of diastereomers, Li₂CO₃ (15 equiv) was used as additive.

^[e]Mass balance was the cyclized product;

^[f]The e.r. values are for the minor diastereomer.

^[g]The result in parenthesis is from a 1 g reaction scale, illustrating the scalability of the method. The corresponding Ritter product^[13] (6%) was also isolated.

^[h]The reactions in entries 15–17 were performed with the quasi enantiomeric (DHQ)₂PHAL catalyst, yielding the enantiomeric product in each case.