Synthesis of poly(phenylacetylene)-block-poly(β-propiolactone) by use of Rh-catalyzed living polymerization of phenylacetylene

Polymerizations Mediated by Well‐Defined Rhodium Complexes

“…Since the seminal contribution from Kishimoto et al . in 1994 and the subsequent pioneering work from Masuda et al., there have clearly been significant advances in the field of catalysis with Rh I complexes and specifically regarding the use of such well‐defined Rh I ‐vinyl and Rh I ‐aryl complexes as catalysts/initiators for the controlled polymerization of alkyne‐based monomers. Although effective catalysts are available for effecting the controlled polymerization of the three monomer families described herein, new, additional, complexes could be prepared and examined; it seems unlikely that the most efficient, active, and broadly applicable Rh complexes for these target applications would have been discovered based on the comparatively limited number of examples reported thus far.…”

“…In the case of the above example, the target BrCPh=C(4‐NMe 2 ‐C 6 H 4 ) 2 precursor was prepared by a multistep procedure and isolated in 10% yield. The synthesis of polyphenylacetylene‐ block ‐poly(β‐propiolactone) copolymers was reported by Kanki, Misumi, and Masuda by employing the [Rh(nbd)Cl] 2 / p‐tert ‐BuMe 2 SiOC 6 H 4 (Ph)C=CPhLi/PPh 3 ternary catalytic system. The use of this silyloxy‐functionalized triarylvinyl species yielded well‐defined polyphenylacetylene bearing the silyloxy functional group at the initiating chain end; its incorporation, as determined by 1 H NMR analysis, was determined to be essentially quantitative.…”

Durch definierte Rhodiumkomplexe vermittelte Polymerisationen

“…Im Falle des obigen Beispiels wurde die Vorstufe BrCPh=C(4‐NMe 2 C 6 H 4 ) 2 in einer mehrstufigen Prozedur in einer Ausbeute von 10 % hergestellt. Die Synthese von Polyphenylacetylen‐ block ‐poly‐β‐propiolacton‐Copolymeren wurde von Kanki, Misumi und Masuda publiziert, wobei das ternäre katalytische System [Rh(nbd)Cl] 2 / p‐tert ‐BuMe 2 SiOC 6 H 4 (Ph)C=CPhLi/PPh 3 Verwendung fand. Die Anwendung dieser Silyloxy‐funktionalisierten Verbindung ergab definierte Polyphenylacetylene, die eine Silyloxyfunktionalisierung am initiierenden Ende trugen; deren Einbau wurde durch 1 H‐NMR‐spektroskopische Analyse als praktisch quantitativ ermittelt.…”

“…Seit der wegweisenden Arbeit von Kishimoto et al . im Jahr 1994 und der folgenden Pionierarbeit von Masuda et al . hat es signifikante Fortschritte im Bereich der Rh I ‐Komplexkatalyse gegeben, speziell bei der Anwendung solcher definierten Rh I ‐Vinyl‐ und ‐Aryl‐Komplexe als Katalysatoren/Initiatoren für die kontrollierte Polymerisation von Alkin‐funktionalisierten Monomeren.…”

Current operator volumes of invasive coronary procedures in medicare patients: Implications for future manpower needs in the catheterization laboratory

“…Thus, we were inspired to apply the Pd catalysts to the synthesis of new end‐functionalized polyacetylenes. Although some articles have discussed the related chemistry,34–42 there have been no such examples achieved with well‐defined Pd catalysts. Here, we report a new strategy for the synthesis of end‐functionalized poly(PA)s using a series of well‐characterized Pd catalysts ( 1a – f , Chart ) and its application to block copolymer synthesis.…”