Gallou, Fabrice (2019) Reactivity of Carbenes in the Aqueous Micelles Containing Palladium Nanoparticles. ACS Catalysis, 9 (12). pp. 10963-10970.

Abstract

Arguably, water, if appropriately used, is the
most sustainable and green solvent for conducting organic synthesis.
Wrongly perceived arguments on the difficulties in water
recycling and generation of more waste, when it is used as a
solvent in synthesis so far posed many hinderances toward its
rampant usage in organic synthesis. Although according to the
Pfizer’s solvent selection guide, water is the most preferred solvent,
still it did not gain the popularity that it deserves. It is an
ideal solvent for chemist safety, process safety, and environmental
safety. Contributions from Kobayashi, Lipshutz, Uozumi,
and our group set the foundation to explore chemistry in
water for highly selective reaction pathways, especially for industrial
applications. Very recently, our group developed an environmentally
benign proline-based amphiphile PS-750-M that
when dissolved in water, instantaneously form nanomicelles
with less-polar interior, unlike other well established amphiphiles.
The rationale behind the design of PS-750-M is the
inclusion of tert-amide functionality inside the micelle to mimic
DMF, DMAc, NMP, and other toxic polar-aprotic solvents
(Figure 1). These toxic solvents have a common tert-amide
group which imparts polarity to these solvent as well as acts as
a residue to participate in secondary interactions in some catalytic
pathways. PS-750-M has been explored on variety of
transformations including those which traditionally require
toxic polar-aprotic solvents. The transformation such as monofluorination
of indoles, which can not be cleanly achieved in
any organic solvent is achieved in PS-750-M. To date, very less
knowledge is available on the behavior of reaction intermediates
in the micellar media. For example, does carbene or carbenoid
exists in the micelle; whether it reacts with micelle or not;
does it impact micellization; can reactions involving carbene intermediates
be successfully achieved in water while leveraging
the positive features of micellar catalysis?

Item Type:	Article
Date Deposited:	21 Jan 2020 00:45
Last Modified:	21 Jan 2020 00:45
URI:	https://oak.novartis.com/id/eprint/40902