Table 2.

The effect of the C4 configuration and type of the C2‐substituent of glycals on the thiol‐ene reaction

Entry	Thiol+Alkene	Product	Temperature (thiol equiv)	Yield [%][a]
1	12 (5 equiv) +2		rt	28
2			0 °C	26
3			−40 °C	56
4			−80 °C	22
5	14 (6–18 equiv) +2		rt[b]	0
6			0 °C[b]	15
7			−40 °C[b]	22
8			−40 °C[c]	26
9			−80 °C[b]	23
10	15 (3 equiv) +2		rt	52
11			0 °C	69
12			−40 °C	41
13	16 (2–3 equiv) +2		rt, (3)	58
14			−80 °C, (2)	86
15	18 (1.5 equiv) +2		−40 °C	35
16			−80 °C	75
17	15 (1.5 equiv) +3		rt	46
18			0 °C	83
19			−80 °C	45
20	14 (6–24 equiv) +3		−20 °C[b]	36
21			−40 °C[b]	50
22			−40 °C[d]	56
23			−80 °C[c]	63
24	18 (1.3 equiv) +3		−40 °C	65
25			−80 °C	33

[a] Isolated yield; by‐product formation was not observed, the low/moderate yields are the results of the low/moderate conversion of the alkenes; [b] 6 equiv of thiol was used; [c] 3×6 equiv of thiol was used; [d] 3×8 equiv of thiol was used.