. Author manuscript; available in PMC: 2015 Nov 3.

Published in final edited form as: Angew Chem Int Ed Engl. 2014 Sep 15;53(45):12172–12176. doi: 10.1002/anie.201406778

Table 3.

Evaluation of the Allylic Electrophile for the Ir-Catalyzed Asymmetric Allylic Substitution with Dienolate 2b.^a


entry	LG	b:l (5a:6a)^b	yield (5a)^c	% ee (5a)^d
1	OCOMe^e	2:5:1	60%	N.D.
2	OCOPh^e	2:1	54%	N.D.
3	OP(O)(OEt)₂	1:1	41%	N.D.
4	OCO₂t-Bu	2:5:1	56%	N.D.
5	OCO₂Me	4:1	67%	N.D.
6	OCO₂CH₂CCl₃	15:1	81%	90%

Reaction conditions: cinnamyl ester (0.2 mmol, 1.0 equiv), silyl dienolate 2b (0.4 mmol, 2.0 equiv), [Ir(cod)Cl]₂ (2 mol%), (S_a,S_c,S_c)-L (4 mol%), KF (1.0 equiv), 18-crown-6 (1.0 equiv), THF (0.4 mL), 50 °C, 12 h.

Branched to linear ratios (5a:6a) were determined by ¹H NMR analysis of the crude reaction mixtures.

Yields of isolated products were listed.

The ee was determined by chiral HPLC analysis. N.D. = Not determined.

Reactions were carried out at 50 °C for 24 h.