Collective Synthesis of 3‑Acylindoles, Indole-3-carboxylic Esters, Indole-3-sulfinic Acids, and 3‑(Methylsulfonyl)indoles from Free (N–H) Indoles via Common N‑Indolyl Triethylborate

A general and direct C3 functionalization of free (N–H) indoles with readily available electrophiles such as acid chlorides, chloroformates, thionyl chloride, and methylsulfonyl chloride via a common N-indolyl triethylborate intermediate is reported. The reaction proceeds smoothly under mild conditions in up to 93% yield. Indoles with substituents at the C2, C4, C5, C6, and C7 positions are well tolerated. The easy accessibility of a variety of important 3-acylindoles, indole-3-carboxylic esters, indole-3-sulfinic acids, and 3-(methylsulfonyl)­indoles demonstrates the high degree of compatibility and practicability of this method.