Table 2.

Transition‐metal bismuthanes act as (pre‐)catalysts in thermally induced radical cyclo‐isomerizations of δ‐iodo‐olefins.

Entry	E	Z	R	R’	t [h]	Yield [%]
1	CH2	CH2	H	H	20	96
2	CH2	CH2	Me	H	3.5	>99[a]
3[b]	O	CH2	H	H	20	83
4	O	CH2	Me	H	10	>99[c]
5	N(C3H5)2	CO	H	H	4.5	>99
6[d]	CH2	CH2	Me	Me	5	90

[a] cis/trans=3.4:1.0; [b] 20 mol % pre‐catalyst; [c] cis/trans=2.7:1.0; [d] T=23 °C.