大家可以看一下工业界里面的研究者主要对学术界的哪些研究感兴趣。Worthy of note is the fact that the procedure was successfully translated under photoflow conditions with a solvent shift to a 1:1 mixture of acetonitrile and DMA.
Worthy of note are the facts that prestirring without irradiation was found to be beneficial to improve yields by favoring activation prior to cross-coupling and that an excess of the acyl donor is used.
3: Direct Synthesis of α-Amino AcidAccess to enantioenriched compounds could be achieved via chirality transfer from pureEllman’s auxiliary with moderate to high enantiomeric excess.4: Meta-Selective C−H Arylation of PhenolsTo circumvent the typical reactivity pattern, this novel C−H arylation occurs via a Bi(V)-mediated electrophilic arylation to reach a disubstituted dienone intermediate. An aryl migration− rearomatization sequence then generates the final phenol product.
5: C4 Alkylation of IsoquinolinesThe transformation is made possible by dearomatization using benzoic acid. Other acids were tested without improvements, although acetic acid also provides an acceptable alternative with lower yield.
6: C(sp2 )−C(sp3 ) Suzuki−Miyaura Cross-CouplingTraditionally, this has achieved the kinds of palladium-mediated transformations that are commonly taught in undergraduate classes, but the use of such expensive raremetal catalysts has obvious drawbacks, particularly on scale.
7: current-controlled nickel-catalyzed multielectrophile electroreductive cross-couplingCross-electrophile coupling methodologies have seen an explosion of interest in recent years and are a favorite tool of medicinal chemists due to the huge number of commercially available aryl and alkyl bromides. Although these reactions are rarely run on scale, recent electrochemical methods have started to remove some of the disadvantages of earlier systems such as the use of a heterogeneous reductant or expensive HAT mediator.
8: site-selective electrochemical oxidation of glycosidesTraditionally, carbohydrate chemistry has been achieved through the dark art of protecting group chemistry, but in recent years significant progress has been made in the site-selective functionalizion of unprotected sugars.Although the reaction can be driven by air rather than pure oxygen, the use of a flammable organic solvent under a noninert atmosphere as well as the high cost of quinuclidine may limit the usefulness of this method on scale.9: photoinduced synthesis of functionalized oxacyclic spirooxindoles via ring expansionstevens-type [1,2]-shift the protocol was demonstrated in flow on a gram scale and successfully exploited for the efficient synthesis of a reported pharmacologically active cb2 agonist.
10: intramolecular ring expansion of 3-silaazetidine with alkynes enabled by pd-catalyzed si−c bond activationSwitching a carbon atom for a silicon is emerging as a promising strategy for the discovery of novel bioactive substances showing benefits with regard to enhanced cell penetration, increased potency, and decreased toxicity.
11: palladium-catalyzed amination of base-sensitive five-membered heteroaryl halides with aliphatic aminesunproductive β-hydride elimination of the amine
Buchwald and coworkers reported a remarkably general system to facilitate these couplings that exploits the combination of a relativelymild base to slow decomposition of the heteroarene with asterically encumbered Pd catalyst to inhibit deactivation through coordination of the heterocycle.
Primary amination of aryl nucleophiles represents a valuable transformation, although it is limited to some degree by the documented safety concerns and/or availability of suitable H2N+ synthons.13: meta c−h functionalization
14: azadiene diels−alder reactionsHowever, while these reactions can often be carried out under milder conditions than conventional Diels−Alder reactions, efforts to catalyze such processes using Lewis acids have often failed due to preferential complexation and nonproductive consumption of the dienophile.
Flow chemistry tubular reactors, due to their short diameter (light path length), maximize incoming photon flux and enable the efficient scale-up of photochemical reactions.
16: ALKYLATION OF C(sp3 )−H BONDSPrimary amination of aryl nucleophiles represents a valuable transformation, although it is limited to some degree by the documented safety concerns and/or availability of suitable H2N+ synthons.
17: red-light-driven c−n cross-couplingDual nickel−photoredox-catalyzed Buchwald−Hartwig amination has been applied in industry by both medicinal chemists and process chemists. However, scalability issues arise when using blue or near-ultraviolet light due to its low penetration through reaction media.
18: peroxygenase catalystHowever, most enzymes catalyzing peroxygenation reactions make use of a cofactor and require nicotinamide cofactor (NAD(P)/H), which limits their use in preparative-scale applications.
19: semipinacol-driven dearomatization of pyridinesThe less reactive Boc2O required at least 5 equiv to reach full conversion, limiting its practicality.
20: asymmetric total synthesis
21: late-stage c(sp3 )−h methylationMao and MacMillan reported the direct introduction of methyl groups via C(sp3 )−H functionalization of a broad array of saturated heterocycles enabled by the merger of decatungstate photocatalysis and a unique nickelmediated bimolecular homolytic substitution (SH2) bond formation.
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