Table 1.

Catalytic enantioselective allylic alkylations with vinylaluminum reagent 3 promoted by NHC–Cu complex derived from 5.^[a]

Entry	Substrate [R]	Yield [%][b]	SN2′:SN2[c]	E:Z[c]	e.r.[d]
1	4a [Ph]	93	>98:2	>98:2	99:1
2	4b [oMeC6H4]	96	>98:2	>98:2	99:1
3	4c [oMeOC6H4]	82	>98:2	>98:2	98:2
4	4d [oNO2C6H4]	89	>98:2	>98:2	>99:1
5	4e [mBrC6H4]	95	>98:2	>98:2	99:1
6	4 f [pClC6H4]	94	>98:2	>98:2	98.5:1.5
7	4g [pNO2C6H4]	87	>98:2	>98:2	97.5:2.5
8	4h [pTsOC6H4]	>98	>98:2	>98:2	99:1
9	4i [pMeC6H4]	92	>98:2	>98:2	>99:1
10	4j [(CH2)2C6H5]	88	>98:2	>98:2	94:6
11	4k [Cy]	88	>98:2	>98:2	94:6

^[a]Reactions were performed under N₂ atmosphere; >98% conversion and <2% iBu addition product in all cases (400 MHz ¹H NMR analysis of unpurified product mixtures).

^[b]Yields of isolated purified products.

^[c]Site-selectivities and alkene stereoselectivities established by analysis of 400 MHz ¹H NMR spectra of product mixtures prior to purification.

^[d]Enantiomer ratios determined by HPLC analysis; see the Supporting Information for details.