Synthesis of Polycyclic Isoindolines via α-C–H/N–H Annulation of Alicyclic Amines
- Award ID(s):
- 1659782
- PAR ID:
- 10454853
- Date Published:
- Journal Name:
- Organic Letters
- Volume:
- 24
- Issue:
- 5
- ISSN:
- 1523-7060
- Page Range / eLocation ID:
- 1224 to 1227
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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null (Ed.)A nontrigonal phosphorus triamide ( 1 , P{N[ o -NMe-C 6 H 4 ] 2 }) is shown to catalyze C–H borylation of electron-rich heteroarenes with pinacolborane (HBpin) in the presence of a mild chloroalkane reagent. C–H borylation proceeds for a range of electron-rich heterocycles including pyrroles, indoles, and thiophenes of varied substitution. Mechanistic studies implicate an initial P–N cooperative activation of HBpin by 1 to give P -hydrido diazaphospholene 2 , which is diverted by Atherton–Todd oxidation with chloroalkane to generate P -chloro diazaphospholene 3 . DFT calculations suggest subsequent oxidation of pinacolborane by 3 generates chloropinacolborane (ClBpin) as a transient electrophilic borylating species, consistent with observed substituent effects and regiochemical outcomes. These results illustrate the targeted diversion of established reaction pathways in organophosphorus catalysis to enable a new mode of main group-catalyzed C–H borylation.more » « less
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