Cobalt-catalyzed deoxygenative triborylation of allylic ethers to access 1,1,3-triborylalkanes

Polyborylated organic compounds have been emerging as versatile building blocks in chemical synthesis. Here we report a selective cobalt-catalyzed deoxygenative 1,1,3-triborylation reaction of allylic ethers with pinacolborane to prepare 1,1,3-triborylalkane compounds. With naturally abundant and/or synthetic cinnamic methyl ethers as starting materials, we have achieved the synthesis of a variety of 1,1,3-triborylalkanes (25 examples). The synthetic utility of these 1,1,3-triborylalkanes is demonstrated through site-selective allylation, protodeborylation, and consecutive carbon-carbon bond-forming reactions. Mechanistic studies including deuterium-labeling and control experiments suggest that this 1,1,3-triborylation reaction proceeds through initial cobalt-catalyzed deoxygenative borylation of allylic ethers to form allylic boronates followed by cobalt-catalyzed 1,1-diborylation of the resulting allylic boronates.

Iodine/water-mediated deprotective oxidation of allylic ethers to access α,β-unsaturated ketones and aldehydes

The first iodine/water-mediated deprotective oxidation of allylic ethers to access α,β-unsaturated ketones and aldehydes was effectively achieved.

Palladium nano-particles as a recyclable catalyst for C–O bond formation under solvent free conditions

Recyclable catalysis: Green, economical and sustainable synthesis of multi-functionalized allylic ethers under solvent free conditions from phenols and vinyl cyclic carbonates using recyclable PdNPs as a catalyst.

One simple Ir/hydrosilane catalytic system for chemoselective isomerization of 2-substituted allylic ethers

One mild and simple Ir/hydrosilane catalytic system for isomerization of 2-substituted allylic ethers with high specificity and chemoselectivity was developed.

Cross-Coupling Reaction of Allylic Ethers with Aryl Grignard Reagents Catalyzed by a Nickel Pincer Complex

A cross-coupling reaction of allylic aryl ethers with arylmagnesium reagents was investigated using β-aminoketonato- and β-diketiminato-based pincer-type nickel(II) complexes as catalysts. An β-aminoketonato nickel(II) complex bearing a diphenylphosphino group as a third donor effectively catalyzed the reaction to afford the target cross-coupled products, allylbenzene derivatives, in high yield. The regioselective reaction of a variety of substituted cinnamyl ethers proceeded to give the corresponding linear products. In contrast, α- and γ-alkyl substituted allylic ethers afforded a mixture of the linear and branched products. These results indicated that the coupling reaction proceeded via a π-allyl nickel intermediate.

A gold(i)-catalysed three-component reaction via trapping oxonium ylides with allenamides

A gold(i)-catalysed three-component reaction between alcohols (and water), α-aryl-α-diazoesters and allenamides is reported, affording tert-allylic ethers (and alcohols), in moderate to excellent yields with excellent geometric selectivity.

Tandem arylation and regioselective allylic etherification of 2,3-allenol via Pd/B cooperative catalysis

An efficient method for the construction of arylated allylic ethers was developed via three-component tandem arylation and allylic etherification of 2,3-allenol with aryl iodides and alcohols.