Here we report that
chiral Mn(I) complexes are capable of H–P
bond activation. This activation mode enables a general method for
the hydrophosphination of internal and terminal α,β-unsaturated
nitriles. Metal−ligand cooperation, a strategy previously not
considered for catalytic H–P bond activation, is at the base
of the mechanistic action of the Mn(I)-based catalyst. Our computational
studies support a stepwise mechanism for the hydrophosphination and
provide insight into the origin of the enantioselectivity.
The curing of bis-methacrylate–styrene resins initiated by the cobalt catalyzed decomposition of cumyl hydroperoxide is monitored at ambient temperatures in situ by EPR and Raman spectroscopy.
Here we report catalytic
asymmetric hydrophosphination
of α,β-unsaturated
carbonyl derivatives using a chiral Mn(I) complex as a catalyst. Through
H–P bond activation, various phosphine-containing chiral products
can be accessed via hydrophosphination of various ketone-, ester-,
and carboxamide-based Michael acceptors.
Olefins are ubiquitous in biologically active molecules and frequently used as building blocks in chemical transformations. However, although many strategies exist for the synthesis of stereodefined
E
-olefines, their thermodynamically less stable
Z
counterparts are substantially more demanding, while access to those bearing an allylic stereocenter with an adjacent reactive functionality remains unsolved altogether. Even the classic Wittig reaction, arguably the most versatile and widely used approach to construct
Z
-alkenes, falls short for the synthesis of these particularly challenging yet highly useful structural motives. Here, we report a general methodology for
Z
-selective synthesis of functionalized chiral alkenes that establishes readily available alkene-derived phosphines as an alternative to alkylating reagents in Wittig olefination, thus offering previously unidentified retrosynthetic disconnections for the formation of functionalized disubstituted alkenes. We demonstrate the potential of this method by structural diversification of several bioactive molecules.
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.