γ,δ,ε-C(sp(3))-H Functionalization through Directed Radical H-Abstraction.
Aliphatic amides are selectively functionalized at the γ- and δ-positions through directed radical 1,5 and 1,6 H-abstractions, respectively. The initially formed γ- or δ-lactams are intercepted by N-iodosuccinimide and trimethylsilyl azide, leading to double and triple C-H functionalizations at the γ-, δ-, and ε-positions. This new reactivity is exploited to convert alkyls into amino alcohols and allylic amines.
†Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
Tao
T
Liu
†Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
Tian-Sheng
TS
Mei
†Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States.
Jin-Quan
JQ
Yu
D000577:Amides / Q000737:chemistry*; D000588:Amines / Q000138:chemical synthesis* / Q000737:chemistry; D000605:Amino Alcohols / Q000138:chemical synthesis* / Q000737:chemistry; D001386:Azides / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D007769:Lactams / Q000138:chemical synthesis / Q000737:chemistry*; D015394:Molecular Structure; D012821:Silanes / Q000737:chemistry*; D013388:Succinimides / Q000737:chemistry*
D000577:Amides; D000588:Amines; D000605:Amino Alcohols; D001386:Azides; D005609:Free Radicals; D007769:Lactams; D012821:Silanes; D013388:Succinimides; C438544:azidotrimethylsilane; C008155:N-iodosuccinimide