Description and purpose
This project aims to develop novel nickel-catalyzed transformations using carbon-dioxide. The modular calix[n]arene scaffold will represent the linchpin to achieve this goal. We aim to develop novel nickel-catalyzed C-H carboxylations for direct functionalizations of calix[4]arene macrocycles. The thus formed chiral calix[4]arenes will be then employed for the enantioselective recognition of biologically relevant amines.
Purpose
We aim to develop novel catalytic methods for the synthesis of inherently chiral calix[4]arenes by nickel-catalyzed C-H carboxylations. The major focus will be to access novel chiral macrocycles with moderate to good enantiomeric excess.
Expected results
We expect to develop novel sustainable catalytic methods for the synthesis of inherently chiral calix[4]arenes by using carbon dioxide as a convenient starting material. The catalytic methods will provide a novel class of macrocycles whose complexation and photophysical properties will be studied in detail.
Achieved results
Preliminary results for nickel catalyzed carboxylations suggested poor reactivities and low enantiomeric ratios. We focused on the development of an enantioselective gold-catalyzed hydroarylation of alkynes for inherently chiral calix[4]arenes. Part of the results acquired have been recently reported in Chemical Communications (RSC) and selected as hot article (high relevant scientific contribution //doi.org/10.1039/D5CC04405G).
