Synthesis of Catechols from Phenols via Pd-Catalyzed Silanol-Directed C–H Oxygenation

Synthesis of catechols using a silanol as activating group.

Here you have a very elegant, simple reaction, that can save your day if you are looking for a cathecol. The trick is simple: get a phenol, prepare a silanol, use Pd(OPiv)2 with PhI(OAc)2, then TBAF and it is over. The reaction works using the silanol as ortho directing group for a C-H activation; the PhI(OAc)2 is, as you would expect, the oxidant. They report 21 examples, with a strikingly good selectivity even over naphtols, though yields are very substrate dependent.

J. Am. Chem. Soc., 2011, 133 (44), pp 17630–17633. See: 10.1021/ja208572v