Table 1 Optimization and control studies for transformation from trithiocarbonates to dithiocarbamates

From: Controlled switching thiocarbonylthio end-groups enables interconvertible radical and cationic single-unit monomer insertions and RAFT polymerizations

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No.

R =

Deviation from Standard Conditions[a]

Yield (%)[b]

1

-OiBu

None

92

2

-COOEt

None

<5

3

-Ph

None

<5

4

-CN

None

8

5

-OiBu

Reaction time: 8 h

36

6

-OiBu

Reaction time: 12 h

74

7

-OiBu

Reaction time: 36 h

91

8

-OiBu

2 eq. TETD

85

9

-OiBu

5 eq. TETD

78

10

-OiBu

without ZnTPP or Red Light

<5

11

-OiBu

Blue Light without ZnTPP

76

12

-OiBu

AIBN at 70 °C

65

13

-OiBu

FcPF6 and DCM

35

  1. aOptimizations were performed on 10 mmol scale using TTC. (1 eq.), TETD (1.1 eq.), and ZnTPP (1 mol %) in acetonitrile (MeCN) under red light irradiation (630 nm) over a period of 24 h. TETD = tetraethylthiuram disulfide, ZnTPP = zinc(II) meso-tetraphenylporphine, AIBN = 2,2’-azobis(2-methylpropionitrile), FcPF6 = ferrocenium hexafluorophosphate.
  2. bIsolated yield.