Platinum(0)-Catalyzed Indolyne Insertion into Bis(pinacolato)diboron Followed by Site-Selective Suzuki-Miyaura Cross-Coupling.

Indolynes are converted into previously unprecedented indole building blocks by platinum(0)-catalyzed insertion into a symmetrically substituted boron-boron bond. The two boron sites in these indoles must be differentiated in a subsequent step, and the 6,7-bis[(pinacolato)boryl]indole was shown to undergo site-selective Suzuki-Miyaura cross-coupling with perfect C7 selectivity. The net reaction is the regioselective installation of two different substituents in the C6 and C7 positions of a 6,7-indolyne precursor.