Dimeric Manganese‐Catalyzed Hydroarylation and Hydroalkenylation of Unsaturated Amides

Abstract

An unprecedented Mn(I)-catalyzed selective hydroarylation and hydroalkenylation of unsaturated amides with commercially available organic boronic acids is reported. Alkenyl boronic acids have been successfully employed for the first time in Mn(I)-catalyzed carbon-carbon bond formation. A wide array of b-alkenylated amide products can be obtained in moderate to good yields, which offers practical access to fiveand six-membered lactams. This protocol has predictable regio-and chemoselectivity, excellent functional group compatibility and ease of operation in air, representing a significant step-forward towards manganese-catalyzed C À C coupling.Supporting information and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.

Manganese-Catalyzed Batch and Continuous Flow Cationic RAFT Polymerization Induced by Visible Light

“…33 It was followed by decomposition of the manganese dimer under the continuous light irradiation, which generates a high vacant state manganese complex. 32 This manganese complex can oxidize 1 to form a cation and manganese−dithiocarbonate complex and may further decompose to other side products, as proposed by the literature. 33 The chain propagating reaction proceeds via the RAFT mechanism, producing well-controlled poly(vinyl ether)s with high chain end fidelity.…”

Dimeric Manganese‐Catalyzed Hydroarylation and Hydroalkenylation of Unsaturated Amides

“…[44,45] The use of Mn(CO) 5 Br can work for hydroarylation and hydroalkenylation, but the corresponding yields are lower. We envisioned that the dimeric Mn 2 (CO) 8 Br 2 [46] is much more prone to generate the 16-electron vacant coordination state (9) than that with Mn(CO) 5 Br. The vacant coordination state of this Ar-Mn intermediate ( 9) readily coordinates with alkenes (1).…”

Rhodium‐katalysierte dealkenylierende Arylierung von Alkenen mit Arylboronverbindungen

“…Ein anderer Ty pbezieht sich auf die Hydroarylierung von Alkenen. [4,5] Bei diesem Ty preagiert der Übergangsmetallkatalysator zunächst mit Hydridrea-genzien, um eine aktive Katalysatorspezies [TM]-H zu erzeugen. Dann interagiert [TM]-H mit Alkenen und Arylboronverbindungen durch einen Hydrometallierungs-und Tr ansmetallierungsprozess in Folge,u me in Arylalkylmetall-Zwischenprodukt zu bilden, das weiter eine reduktive Eliminierung durchläuft, um ein hydroaryliertes Produkt zu liefern (Schema 1b).…”