Table 1.

Optimization of the titanocene(III) chloride catalyzed reductive cyclization of anilines.^a,^b

entry	epoxide	Cp2TiCl2 (mol %)	Mn (equiv)	concentration [M]	R1	R2	product(s), yield
1	4a	10	0.80	0.03	Ph	H	5a:6a (3:1)c,d
2	4b	10	0.65	0.03	Ph	CH3	5b, 82%d
3	4b	10	0.65	0.03	Ph	CH3	5b, 84%e
4	4c	10	1.5	0.1	Cbz	CH3	5c:7c (2:1)f
5	4c	3	1.5	0.1	Cbz	CH3	8c, 63%g
6	4b	3	1.5	0.1	Ph	CH3	5b, 89%
7	4a	3	1.5	0.1	Ph	H	5a:6a (3.8:1), 87%
8	4c	3	1.5	0.1	Cbz	CH3	5c, 14%h
9	4c	3	0	0.1	Cbz	CH3	5c, 0%
10	4c	0	1.5	0.1	Cbz	CH3	5c, 0%

^aFor epoxide preparation, see Supporting Information.

^bAll reactions were performed in degassed THF heated at reflux unless otherwise noted.

^cYield not determined; product ratio was determined by GC analysis of crude reaction mixtures.

^dReaction was performed in degassed THF at room temperature using sonication.

^eReaction was performed in degassed THF at room temperature using magnetic stirring.

^fYield not determined; product ratios were determined by ¹H NMR analysis of crude reaction mixtures.

^gYield was determined over 2 steps.

^hStarting material 4c was recovered in 43% yield.