TY - JOUR
AU - Bonifazi, Davide
AB - The present Protocol
describes the application of the catalyst-transfer
macrocyclization (CTM) reaction, focusing on the synthesis of aza[1n]paracyclophanes (APCs). APCs are fully π-conjugated
shape-persistent macrocycles with potential supramolecular chemistry
and materials science applications. This method leverages the Pd-catalyzed
Buchwald–Hartwig cross-coupling reaction to selectively form
π-conjugated cyclic structures, a significant advancement due
to its efficiency, versatility, and scalability. Overall, this Article
highlights the following attributes of the CTM method: a) Efficiency
and Yield: The CTM method works at mild temperatures (40 °C)
and short reaction times (≥2 h), producing high yields of APCs
(>75% macrocycles). It avoids the typical high-dilution conditions,
making it more practical for large-scale applications. b) Versatility:
The method allows the synthesis of APCs with diverse endocyclic and
exocyclic functionalities and ring sizes (typically from 4- to 9-membered
rings), expanding the chemical space for these compounds. This flexibility
is crucial for tailoring APC properties for specific applications.
c) Scalability and Reproducibility: Unlike many macrocyclization reactions,
which require highly dilute conditions, CTM can perform under concentrated
regimes (35–350 mM), making it more suitable for large-scale
applications. d) Applications in Materials Science: APCs are noted
for their potential in optoelectronic applications due to their π-conjugated
structures, which are helpful in organic semiconductors, light-harvesting
systems, and other advanced materials. This approach addresses the
challenge of complicated multistep syntheses that have hindered the
widespread integration of APCs into functional devices. A step-by-step
guide to preparing exemplary APCs, including troubleshooting, is provided
with photographic illustrations.
TI - Catalyst-TransferMacrocyclization Protocol: Synthesisof π-Conjugated Azaparacyclophanes Made Easy
JF - JACS Au
DO - 10.1021/jacsau.5c00109
DA - 2025-03-07
UR - https://www.deepdyve.com/lp/pubmed-central/catalyst-transfermacrocyclization-protocol-synthesisof-conjugated-TdjNUv96UW
SP - 1482
EP - 1498
VL - 5
IS - 3
DP - DeepDyve
ER -