Facile Synthesis of Sequence‐Defined Oligo(Dimethylsiloxane‐ co ‐Diphenylsiloxane)s

1,1,3,3,5,5,7,7‐Octamethyltetrasiloxane ( H MD 2 M H ), which is reported to release Me 2 SiH 2 via a B(C 6 F 5 ) 3 ‐catalyzed redistribution, acts as a good Me 2 SiH 2 precursor in the B(C 6 F 5 ) 3 ‐catalyzed dehydrocarbonative condensation of alkoxysilanes. A series of oligo(dimethylsiloxane‐ co ‐diphenylsiloxane)s that are uniformly sized and sequence‐defined at the atomic level are synthesized by a one‐pot controlled iteration of a B(C 6 F 5 ) 3 ‐catalyzed dehydrocarbonative condensation of alkoxysilanes with H MD 2 M H or Ph 2 SiH 2 and a B(C 6 F 5 ) 3 ‐catalyzed hydrosilylation of carbonyl compounds, followed by the subsequent B(C 6 F 5 ) 3 ‐catalyzed dehydrogenative condensation of silanols.