Table 1.

Development of the first stereocontrolled SM coupling of chiral haloallenes.

Entry	2	R	X	ligand	3	% stereoretention a,b
1	(R)-2a	t-Bu	CI	PPh3	(S)-3a	−78
2	(R)-2b	t-Bu	Br	PPh3	(S)-3a	−78
3	(R)-2c	t-Bu	I	PPh3	(R)-3a	72
4	(R)-2d	3-pentyl	I	PPh3	(R)-3b	58
5	(R)-2e	n-pentyl	I	PPh3	(R)-3c	25
6	(R)-2c	t-Bu	I	PFur3	(R)-3a	80
7	(R)-2c	t-Bu	I	PCy3	(R)-3a	50
8	(R)-2c	t-Bu	I	Pt-Bu2Me	(R)-3a	71
9	(R)-2c	t-Bu	I	Po-Tol3	(R)-3a	91
10	(R)-2c	t-Bu	I	Pt-Bu3	(R)-3a	93
11	(R)-2c	t-Bu	I	XPhos	(R)-3a	91
12c	(R)-2c	t-Bu	I	XPhos	(R)-3a	>99d
13c	(R)-2d	3-pentyl	I	XPhos	(R)-3b	>99
14c	(R)-2e	n-pentyl	I	XPhos	(R)-3c	85

^a% stereoretention = ee product/ee starting material (chiral GC, average of 2 runs); negative values reflect net stereoinversion.

^bUnoptimized GC yields ranged from 10–83%.

^cHexane:THF:H₂O 9:1:1 was used as solvent.

^dIsolated yield = 61%.