[238], and carbene insertion into N–H bond of amines [239]. Ru 2 (OAc) 4 Cl (93) and
Ru 2 (esp) 2 Cl (94) (Scheme 49) were shown to promote oxidation of organic sulfides
by TBHP at ambient condition either in acetonitrile or in neat (solvent-free)
Catalyst
Yield, %
(40 °C)
Product ratio
88a
88b
E-89
Z-89
37
85
100
0
0
0
2
45
14
0
11
75
3
26
18
0
15
67
7
28
20
0
18
62
Scheme 47 Carbenoid vs vinylogous reactivity
Catalyst
90:91 ratio Z/E ratio of 90
Yield, %
1
>98:2
2:1
54
2
>98:2
2:1
37
6
>98:2
2.4:1
40
37
33:67
2.5:1
81
92
68:32
1.1:1
60
Scheme 48 Vinylogous reactivity in reaction with cyclopentadiene
Reactivity and Catalysis at Sites Trans to the [Ru–Ru] Bond
89
Ru 2 (esp) 2 Cl (94) (Scheme 49) were shown to promote oxidation of organic sulfides
by TBHP at ambient condition either in acetonitrile or in neat (solvent-free)
Catalyst
Yield, %
(40 °C)
Product ratio
88a
88b
E-89
Z-89
37
85
100
0
0
0
2
45
14
0
11
75
3
26
18
0
15
67
7
28
20
0
18
62
Scheme 47 Carbenoid vs vinylogous reactivity
Catalyst
90:91 ratio Z/E ratio of 90
Yield, %
1
>98:2
2:1
54
2
>98:2
2:1
37
6
>98:2
2.4:1
40
37
33:67
2.5:1
81
92
68:32
1.1:1
60
Scheme 48 Vinylogous reactivity in reaction with cyclopentadiene
Reactivity and Catalysis at Sites Trans to the [Ru–Ru] Bond
89