Present methods to synthesize 1,3-dithiane molecules require either harsh reaction conditions or highly specialized reagents. We have developed a catalytic dithioacetalization process that directly gains access to the corresponding 1,3-dithianes using aldehydes and 2-chloro-1,3-dithiane in a highly efficient manner. This methodology is beneficial due to mildness of the reaction conditions, and the dithioacetaliation process results in good to excellent yields by using 15 mol % of an iron catalyst.
An alternative method to an iron-catalyzed radical oxidative cross-coupling reaction followed by 2-chloro-1,3-dithiane and aryl olefins for the synthesis of β-chloro substituent 1,3-dithiane products is presented. The described method has the advantage of mildness of the reaction conditions and tolerates a variety of functional groups. Preliminary mechanistic studies have confirmed the first example of a coupling of 1,3-dithiane with unactivated alkenes that proceeds via an iron-catalyzed oxidative radical intermediate along the reaction pathway.
An efficient metal-free Mizoroki-Heck type reaction of di- and tri-substituted alkenes with 2-chloro-dithiane has been developed under ambient pressure of air or using a relatively low loading of BF3·Et2O. This study represents a new environmentally friendly method for the syntheses of dithianyl-substituted alkene derivatives via a radical oxidative coupling process.
Dithianes are versatile umpolung intermediates in organic synthesis but have rarely been employed in radical cross-coupling reactions. Here we describe the oxidative coupling method for alkyne difunctionalization under metal-catalyst-free conditions. The efficient protocol directly affords a variety of β-ketodithianes in good to excellent yields with high regioselectivities. It provides a general pathway for accessing valuable dithianes with controlled formation of a new C-C bond and a C-O bond via a radical coupling pathway.
Atom transfer radical addition (ATRA) of 2-chlorodithiane onto aryl alkynes through the use of di-tert-butyl peroxide as an oxidant at room temperature directly affords a variety of synthetically valuable β-chloro-(Z)-vinyl dithianes in good yields with high regioselectivities and without the assistance of any transition metals. It provides an operationally simple pathway to access vinyl dithianes with controlled formation of a new C(sp(2) )C bond and a C(sp(2) )Cl bond.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.