Main-group organometallics are useful intermediates for the chemoselective
and diastereoselective C-C bond formation. The boron-zinc exchange is a uni
que way for preparing chiral secondary alkylzinc reagents which are configu
rationally stable over a wide temperature scale, Coupled with the thermal r
earrangement of tertiary organoboranes, a broad range of open-chain and cyc
lic polyfunctional molecules have been prepared. In addition, several examp
les of a diastereoselective remote C-H activation have been studied. The se
cond part shows that the main-group metallic alkoxides such as t-BuOK can b
e used for the performance of catalytic reactions such as a new indole synt
hesis.