A Facile Route to Aryl Boronates: Room‐Temperature,Copper‐Catalyzed Borylation of Aryl Halides with Alkoxy Diboron Reagents

A simple but effective copper‐catalyzed borylation of aryl halides, including electron‐rich and sterically hindered aryl bromides, with alkoxy diboron reagents occurs under mild conditions (see scheme). Preliminary DFT studies of the mechanism suggest that σ‐bond metathesis between a copper–boryl intermediate and the aryl halide generates the aryl boronate product.

     

Zinc‐Catalyzed Borylation of Primary,Secondary and Tertiary Alkyl Halides with Alkoxy Diboron Reagents at Room Temperature

A new catalytic system based on a Zn^II NHC precursor has been developed for the cross‐coupling reaction of alkyl halides with diboron reagents, which represents a novel use of a Group XII catalyst for C? X borylation. This approach gives borylations of unactivated primary, secondary, and tertiary alkyl halides at room temperature to furnish alkyl boronates, with good functional‐group compatibility, under mild conditions. Preliminary mechanistic investigations demonstrated that this borylation reaction seems to involve one‐electron processes.     

A Dual Palladium and Copper Hydride Catalyzed Approach for Alkyl–Aryl Cross‐Coupling of Aryl Halides and Olefins

We report an efficient means of sp²–sp³ cross coupling for a variety of terminal monosubstituted olefins with aryl electrophiles using Pd and CuH catalysis. In addition to its applicability to a range of aryl bromide substrates, this process was also suitable for electron‐deficient aryl chlorides, furnishing higher yields than the corresponding aryl bromides in these cases. The optimized protocol does not require the use of a glovebox and employs air‐stable Cu and Pd complexes as precatalysts. A reaction on 10 mmol scale further highlighted the practical utility of this protocol. Employing a similar protocol, a series of cyclic alkenes were also examined. Cyclopentene was shown to undergo efficient coupling under these conditions. Lastly, deuterium‐labeling studies indicate that deuterium scrambling does not take place in this sp²‐sp³ cross coupling, implying that β‐hydride elimination is not a significant process in this transformation.     

Copper‐Catalyzed 1,2‐Methoxy Methoxycarbonylation of Alkenes with Methyl Formate

Reported here is a copper‐catalyzed 1,2‐methoxy methoxycarbonylation of alkenes by an unprecedented use of methyl formate as a source of both the methoxy and the methoxycarbonyl groups. This reaction transforms styrene and its derivatives into value‐added β‐methoxy alkanoates and cinnamates, as well as medicinally important five‐membered heterocycles, such as functionalized tetrahydrofurans, γ‐lactones, and pyrrolidines. A ternary β‐diketiminato‐Cu^I‐styrene complex, fully characterized by NMR spectroscopy and X‐ray crystallographic analysis, is capable of catalyzing the same transformation. These findings suggest that pre‐coordination of electron‐rich alkenes to copper might play an important role in accelerating the addition of nucleophilic radicals to electron‐rich alkenes, and could have general implications in the design of novel radical‐based transformations.     

Copper‐Catalyzed Borylacylation of Activated Alkenes with Acid Chlorides

A method for the copper‐catalyzed borylacylation of activated alkenes is presented. The reaction involves borylcupration of the alkene, followed by capture of the generated alkyl–copper intermediate with an acid chloride. The reactions operated with low catalyst loading and generally occurre within 15 min at room temperature for a range of activated alkenes. In the case of vinyl arenes, enantioselective borylacylation was possible.     

Copper-Catalyzed Borylation of Acyl Chlorides with an Alkoxy Diboron Reagent: A Facile Route to Acylboron Compounds

Herein, the copper-catalyzed borylation of readily available acyl chlorides with bis(pinacolato)diboron, (B₂pin₂) or bis(neopentane glycolato)diboron (B₂neop₂) is reported, which provides stable potassium acyltrifluoroborates (KATs) in good yields from the acylboronate esters. A variety of functional groups are tolerated under the mild reaction conditions (room temperature) and substrates containing different carbon-skeletons, such as aryl, heteroaryl and primary, secondary, tertiary alkyl are applicable. Acyl N-methyliminodiacetic acid (MIDA) boronates can also been accessed by modification of the workup procedures. This process is scalable and also amenable to the late-stage conversion of carboxylic acid-containing drugs into their acylboron analogues, which have been challenging to prepare previously. A catalytic mechanism is proposed based on in situ monitoring of the reaction between p-toluoyl chloride and an NHC-copper(I) boryl complex as well as the isolation of an unusual lithium acylBpinOBpin compound as a key intermediate.