Efficient One-Pot Synthesis Of End-Functionalized Trans-Stereoregular Polydiene Macromonomers

End-functionalized 1,4-trans-polydienes (isoprene and myrcene) were prepared by means of a neodymium-mediated continuous polymerization-functionalization process. A chain transfer stage was essential to get a high level of functionalization of the polymer. The living 1,4-trans-stereoregular polymer chain was reacted with benzophenone to afford up to 97% -CPh2OH end-group with isoprene, while in the case of myrcene, using the same strategy afforded 1,4-trans-polymyrcene with a functionalization rate of 83%. The strategy was validated with complementary functionalization experiments using benzaldehyde and styrene oxide, both affording 95% end-capped trans-stereoregular polydienes.