[reaction: see text] The ortho metalation (RLi/THF/-93 degrees C) of 3 followed by quench with a variety of electrophiles constitutes a new general route to substituted aryl O-sulfamates 4a-k. The Kumada-Corriu cross-coupling of O-sulfamates 4e, 4n-s, and 6a with Grignard reagents gives biaryls 9a-m, and the use of 2-halo and boron derivatives 4h, 4i, and 4k for Suzuki-Miyaura cross-coupling and generation of benzynes leads to naphthols 7a and 7b. A relative metalation ranking of the OSONEt(2) is reported.

No abstract

[reaction: see text] A general alkyllithium/LDA-mediated rearrangement of N-carbamoyl diarylamines 7a-g into the anthranilamides 8a-g and 9a-g (Table 1) is presented and applied to a regioselective efficient construction of acridone (17) and pyranoacridone (18) alkaloids (Scheme 4).

The first Directed ortho Metalation (DoM) reaction of aryl O-carbamates on polystyrene-divinylbenzene (PS-DVB) resin using a trityl linker is described. Using low temperatures and short metalation times, a range of electrophiles have been introduced to give, after cleavage from support, substituted benzyl alcohols in high purity.

No abstract