A practical and highly efficient method for the construction of a variety sulfonamides mediated by I₂ was demonstrated. The reaction proceeds readily at room temperature using sodium sulfinates amines or ammonia in water metal-, base-, ligand-, additive-free protocol. Primary, secondary tertiary were obtained good to excellent yields with broad range substrate tolerability.

Abstract An original and efficient copper‐catalyzed 1,6‐hydrodifluoroacetylation of para ‐quinone methides with difluoroalkyl bromides has been described bis(pinacolato)diboron (B 2 pin ) as reductant. In this reaction, a new C( sp 3 )–CF bond is constructed under smart conditions. A broad substrate scope ( p ‐QMs) make protocol very practical attractive. Preliminary mechanistic studies manifested that radical pathway was involved in reaction. Also the presence diboron reagent an essential...

An efficient and general method for C(sp(2))-H difluoroalkylation of aldehyde derived hydrazones via a Cu(II)/B2pin2-catalyzed reaction between difluoroalkyl bromides was developed. In this reaction, both aromatic aliphatic difluoroalkylated could be achieved in good to excellent yields. For some heteroaromatic hydrazones, two fluoroacetates introduced onto the final products. A preliminary mechanism study manifested that radical SET pathway involved reaction. addition, catalytic diboron...

An original and efficient synthesis of 3,3-difluoro-2-oxindole derivatives has been developed via copper/B2pin2-catalyzed difluoroacetylation aniline C-H activation followed by intramolecular amidation. In this method, amino groups in primary, secondary or tertiary anilines act as directing groups, providing ortho-difluoroacetylated products regioselectively. And the first two cases, further amidation affords a one-pot strategy. This method facilitates compound A potent selective EP3...

A copper-catalyzed hydrofluoroacetylation of arylacetylenes or alkynyl carboxylic acids with bromofluoroacetates was developed. The reaction shows excellent stereoselectivity to afford fluoroacetylated alkenes in good yields a broad substrate scope.

We reported a synergistic Pd/Cu catalyzed enantioselective decarboxylative allylation of vinylethylene carbonates with glycine iminoesters, which provides facile access to non-proteinogenic diverse trisubstituted allylic amino acid derivatives in high yields, exclusive regioselectivities and excellent stereoselectivities. This reaction tolerates wide range γ β-aryl substituted either electron-donating or electron-withdrawing groups. Significantly, this method was proven be sufficient the...

We have established a practical and concise method for the straightforward access of universal deuterated methylthiolating reagent through one-pot gram-scale operation under mild conditions. This odourless electrophilic SCD3 was widely applied to react with numerous representative nucleophiles approached various valuable analogues excellent levels deuterium content (>99% D). The divergent further transformations were smoothly carried out obtain significant derivatives different oxidative...

We developed an asymmetric decarboxylative allylic alkylation of vinylethylene carbonates with α-fluoro pyridinyl acetates through a synergistic palladium/copper catalysis. This protocol provides chiral alcohol carbon–fluorine quaternary stereogenic centers in good yield enantioselectivities and excellent regioselectivities. The utility this approach was further demonstrated via gram-scale experiment derivatizations the product.

An effective method for the synthesis of dihydropyrans through synergistic palladium and chiral phosphonic acid catalysis was reported. This protocol proceeded under mild reactions provided in up to 87% yield 97% ee.

Herein, we report a modular α-monoalkylation of cyclic 1,3-dicarbonyls with cyclopropyl alcohols through iodonium ylide strategy. This approach is general, base-free, operationally simple, and suitable for various medically important (hetero)cyclic 1,3-dicarbonyls. A wide range alcohols, easily prepared from feedstock chemicals, can serve as complement alkylating agents. Importantly, the newly formed carbonyl groups in resulting products provide versatile platform numerous synthetic applications.

Herein we report the palladium-catalyzed regio- and stereoselective cross-coupling of vinylethylene carbonates with ketimine esters to construct allylic amino acid scaffolds. This operationally simple protocol furnished (Z)-tri- tetra-substituted derivatives in good excellent yields distinguished geometric control under mild reaction conditions proved be sufficient large-scale synthesis while retaining reactivity stereoselectivity, highlighting practical value this transformation.

We have developed a methodology for the greatly efficient construction of significant 2,3-dihydrobenzofuran scaffolds bearing quaternary carbon center at C2 position by means [4 + 1] annulation reactions between p-quinone methides and α-aryl diazoacetates as C1 synthons through organocatalysis readily accessible TfOH catalyst under mild transition metal-free conditions. This protocol furnishes an operationally simple swift process free assembly diverse highly functionalized...

Abstract A palladium‐catalyzed highly stereoselective sulfonylation of vinylethylene carbonates for the precise synthesis structurally diverse ( Z )‐allylic sulfones was achieved with excellent regioselectivity and stereoselectivity / E ratio, up to 99 : 1). This protocol used inexpensive sodium sulfinates as sulfonyl sources construct valuable in good yields. The controlling experiment suggested that hydroxyl proton came from α‐hydrogen sulfone group through 1, 5‐H shift.

Enol ether structural motifs exist in many highly oxygenated biologically active natural products and pharmaceuticals. The synthesis of the geometrically less stable Z-enol ethers is challenging. An efficient Z-selective oxidative isomerization process allyl catalyzed by a cobalt(II) (salen) complex using N-fluoro-2,4,6-trimethylpyridinium trifluoromethanesulfonate (Me3NFPY•OTf) as an oxidant has been developed. Thermodynamically were prepared excellent yields with high geometric control....

We report the room-temperature Pd-catalyzed methoxy-carbonylation with high branched selectivity using a new class of bisphosphine-picolinamide ligands. Systematic optimization ligand structures and reaction conditions revealed significance both picolinamide bisphosphine groups in backbone. This strategic design was leveraged to deliver various α-substituted acrylates good excellent yields.

Palladium-catalyzed linear-selective hydroesterification of vinyl arenes with alcohols enabled by diphosphine ligands derived from bis[2-(diphenylphosphino)ethyl]amides has been developed. A variety 3-arylpropanoate esters were obtained in high yields and regioselectivity. The robustness this methodology was further demonstrated the efficient gram-scale synthesis ethyl 3-phenylpropanoate as a precursor to hydrocinnamic acid.

A multisubstituted tetrahydrofuran building block bearing three vicinal chiral carbon centers widely exists in a broad spectrum of bioactive natural products, and the development efficient convenient methods to establish this skeleton remains challenging task. Herein, we have developed an method for construction significant scaffolds α-quaternary stereocenters through Pd-catalyzed asymmetric [3 + 2] annulation vinylethylene carbonates with alkenes installed on cyclic N-sulfonyl imines....

Synergistic palladium/copper catalysis for asymmetric allylic alkylation of vinylethylene carbonates with aldimine esters has been developed the synthesis α-quaternary (Z)-trisubstituted amino acids under mild conditions. This methodology features broad substrate compatibilities in yields up to 87% and 94% ee. A facile scale-up straightforward conversion 1,2,3,5-tetrasubstituted pyrrole 1,2,5,6-tetrahydropyridine bearing chiral quaternary carbon centers verifies synthetic utility this method.

The asymmetric synthesis of (−)-chloramphenicol, (−)-azidamphenicol, and (+)-thiamphenicol its (+)-3-floride, (+)-florfenicol, is reported. This approach toward the amphenicol antibiotic family features two key steps: (1) a cinchona alkaloid derived urea-catalyzed aldol reaction allows highly enantioselective access to oxazolidinone gem-diesters (2) continuous flow diastereoselective decarboxylation thermally stable form desired trans-oxazolidinone monoesters with adjacent stereocenters that...

Abstract A first simple palladium catalyzed allylation of vinylethylene carbonates with β ‐ketophosphonates has been developed. This method provides access to ( Z )‐tri‐ and tetrasubstituted homoallylic phosphonates exclusive regioselectivity, chemoselectivity )‐stereoselectivity. The reaction tolerates a wide substrate scope electron‐donating electron‐withdrawing groups works well on the gram scale.

Abstract An asymmetric allylation of cyclic ketimine esters with vinylethylene carbonates was accomplished through a Pd/Cu dual catalysis system under mild condition, providing range trisubstituted allylic 2 H ‐pyrrole analogues bearing chiral quaternary stereogenic center in high yields (up to 92% yield) and excellent regioselectivities enantioselectivities 96% ee). A gram‐scale operation also conducted efficiency without erosion enantioselectivity stereoselectivity. magnified image