Ms. Loft et al., SYNTHETIC APPLICATIONS OF ARENETRICARBONYLCHROMIUM(0) COMPLEXES - THESYNTHESIS OF POLYFUNCTIONALISED THIOPHENES, Journal of the Chemical Society. Perkin transactions. I, (2), 1995, pp. 97-104
Lithiation of thiophenetricarbonylchromium(o) complexes with butyllith
ium occurs preferentially at C-2/5 but when these are blocked, 3/4 lit
hiation is facile. Combinations of a bulky silyl ((Pr3Si)-Si-i or Bu(t
)'Me(2)Si) blocking group at C-2/5 and remote lithiation/electrophilic
quench of C-3/4 followed by desilylation/lithiation/electrophilic que
nch allowed the synthesis of 2,3-. 2,3,5- and 2.3,4,5-polysubstituted
thiophene complexes and their derived free thiophenes.