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. Author manuscript; available in PMC: 2017 Aug 18.
Published in final edited form as: J Am Chem Soc. 2016 Jan 6;138(2):696–702. doi: 10.1021/jacs.5b12308

Table 3.

Studies of the Electronic Site Selectivity of the Aliphatic C–H Chlorination with N-Chloroamide 1.

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entry reagents % selectivity of chlorination
α β γ δ ω
MeO2C —CH2—CH2—CH2—CH2—CH3
1 SO2Cl2, BPO, 85 °C — 12.1 37.7 42.0 8.2
2 Mn(TPP)Cl/NaOCl — 8.2 43.7 44.8 3.3
3 chloroamide 1, BPO, 65 °C — 10.8 37.9 42.4 8.9
4 chloroamide 1, hv, 1 equiv Cs2CO3, 55 °C 3.6 4.6 19.7 57.6 14.4
(83% combined yield)
substrate (1 equiv) % selectivity of chlorination combined yield (%)
α β γ δ ω
EWG —CH2—CH2—CH2—CH2—CH3
5 graphic file with name nihms874319t11.jpg
17 		— — 4.9 81.2 13.9 80
6 graphic file with name nihms874319t12.jpg
18 		— — 15.0 65.9 19.1 79
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19 		9.2 5.7 15.3 56.9 12.9 74
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20 		— 9.0 19.8 57.3 13.8 89
9 graphic file with name nihms874319t15.jpg
21 		3.5 5.9 16.2 56.2 18.1 86
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22 		23.9 65.5 7.5 70

All reactions were performed with [substrate]0 = 1.0 M in PhH at rt under visible light irradiation with 1 equiv of substrate and 2 equiv chloroamide. Yields and selectivities determined by GC analysis.