Organosulfur compounds have a pivotal role in the functionalities of many natural products, pharmaceuticals and organic materials. For these reason, the search for new methodologies for the formation of carbon–sulfur...
This review summarizes the most relevant advancements made in the photocatalyzed synthesis of sulfones, thioethers and sulfonamides from 2017 to the beginning of 2021. Synthetic strategies towards the construction of sulfur-carbon bonds are discussed together with the proposed reaction mechanisms. Interestingly, sulfured-based functional groups, which are of fundamental importance for the pharmaceutical field, can be assembled by photocatalysis in an easy and straightforward way in milder reaction conditions employing less toxic and expensive sulfur sources in comparison with common strategies
Here, we present an intriguing photoinduced chloroamination
cyclization
of allenes bearing a tethered sulfonylamido group to afford 2-(1-chlorovinyl)pyrrolidines
and related heterocycles in the presence of N-chlorosuccinimide
(NCS) as the chlorine source. An in depth experimental and computational
mechanistic study revealed the existence of multiple reaction pathways
leading to a common nitrogen centered radical (NCR). This key NCR
can be, in fact, originated from (a) the oxidation of the deprotonated
allene by the photoexcited state of the Ru-catalyst and (b) the photodissociation
of the in situ formed N-chloroallene. The NCR formation
triggers an intramolecular cyclization to a highly reactive pyrrolidine
vinyl radical, which upon chlorination delivers the final product.
Thus, NCS plays a dual role, serving both as an activator of the sulfonamido
functionality and as the chlorinating agent.
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