Table 2.

entry	allylic alcohol	alkyne	yield (%)	E:Z	1,4-dienea, b, c
1	23; R = H	7	41	–	24; R = H
2	25; R = Me		66	–	26; R = Me
3	27	7	53	–	28
4	29; R1 =H, R2 =Me	7	59	–	30
5	31; R1 =Me, R2 =H		67	–
6	32	7	57	–	33
7	34; R=Ph	7	78	1:1	35; R=Ph (E/Z=1:1)
8	36; R=Et		67	1:1	37; R=Et (E/Z=1:1)
9	38	7	72	≥20:1	39
10	38	40	77	≥20:1	41d
11	38	42	59	≥20:1	43e
12	44; R1=Me, R2=H	7	67	1:1	45; R1, R2=(CH2)2OPMB
13	46; R1=H, R2=Me	42	59	8:1	47e; R1=(CH2)2Ph, R2=TMS
14	48	7	59	≥20:1	49

^aReaction conditions for cross coupling: alkyne (1.0 eq), ClTi(Oi-Pr)₃, PhMe, C₅H₉-MgCl, −78 to −35 °C, then recool to −78 °C, add Li-alkoxide of allylic alcohol (1.0 eq) (−78 to 0 °C).

^bAll 1,4 diene products were isolated as a single olefin isomers.

^cNo evidence was found for the production of regioisomeric products.

^dIn the formation of the titanium–alkyne complex, the temperature was kept under −55 °C (see supporting information for details).

^err ≥ 20:1.