Multicomponent
tandem reactions (MCTRs), with multiple bonds formed in a highly concise
fashion in a single vessel, have been noted as one of the most powerful
and popular synthetic strategies in modern organic chemistry. Attracted
by their operational simplicity, synthetic efficiency, high atom economy,
and environmental benefit, the MCTRs and the corresponding multicomponent
tandem polymerizations (MCTPs) of alkynes, carbonyl chlorides, and
aliphatic/aromatic thiols were developed. By combining the Sonogashira
coupling reaction between alkynes and carbonyl chlorides, and the
hydrothiolation reaction of electron-deficient alkynone intermediates,
high atom economy was achieved in such one-pot, two-step, three-component
reactions/polymerizations. The MCTPs can proceed efficiently under
mild conditions near room temperature to afford sulfur-rich polymers
with high molecular weight, high yield, high regioselectivity, and
good stereoselectivity. Through the MCTPs of different combination
of monofunctional and bifunctional monomers, polymers with tunable
backbone structures and photophysical properties can be obtained.
These polymers generally possess good solubility and film-forming
ability. Their thin films enjoy high refractivity, and their photosensitivity
enables easy modulation of the thin film refractive indices.