We describe a cobalta-electro-catalyzed enantioselective C–H annulation of arylphosphinamides with alkynes for P-stereogenic compounds via desymmetrization and kinetic resolution processes.

A series of Mn(I) catalysts containing imidazole-based chiral PNN tridentate ligands with controllable "side arm" groups have been established, enabling the asymmetrical hydrogenation unsymmetrical benzophenones outstanding activity (up to 13 000 TON) and excellent enantioselectivity >99% ee). This protocol uses K2CO3 as an industrially desirable base features a wide substrate scope functional group tolerance. Moreover, imine in catalyst is crucial for accessing high activities good...

We described here the first example of cobalt-electro-catalyzed enantioselective C–H acyloxylation arylphosphinamides with carboxylic acids to generate P-stereogenic scaffolds.

Abstract The first example of cobalt‐catalyzed C( sp 2 )−H carbonylation benzylamines using a traceless directing group is reported, which was successfully applied to the synthesis N −unprotected iso‐indolinones through direct C−H/N−H bonds activation. This protocol tolerates variety functional groups and provides facile efficient method for formal (+)‐garenoxacin. magnified image

A series of air-stable, easily accessible tridentate ferrocene-based diamine-phosphine sulfonamide (f-diaphos) ligands were successfully developed for iridium-catalyzed asymmetric hydrogenation ketones. The f-diaphos exhibited excellent enantioselectivity and superb reactivity in Ir-catalyzed ketones (for arylalkyl ketones, (S)-selectivity, up to 99.4% ee, 100 000 TON; diaryl (R)-selectivity, 98.2% 10 TON). This protocol could be conducted on gram scale, thereby providing a chance various drugs.

Abstract An atom and step economy cascade trifluoromethylation/cyclization of unactivated alkene with Langlois reagent as a CF 3 source is described. A variety polycyclic quinazolinones were successfully synthesized in 52–81% yields under transition metal‐ oxidant‐free conditions. The used this strategy possesses the advantages bench‐stablity, cost‐effectivity high‐efficiency. Additionally, gram‐scale reaction, broad substrate scope good functional group tolerance demonstrated synthetic...

Electrocatalysis for the controllable coupling of thiols with DCE was achieved to generate value-added β-chloro-tethered sulfur compounds in batch and flow.

Regional and stereoselective construction of spirooxindole-fused spiropyrazolones containing contiguous three stereogenic centres <italic>via</italic> [3 + 2] annulation catalyzed by ferrocene derived bifunctional phosphine.

The first example of manganese-catalyzed asymmetric transfer hydrogenation N-heteroaromatics in water with good yields and ee up to 99%.

Despite a few successful examples, controlling the enantioselectivity in asymmetric synthesis of non-C2-symmetric biaryldiols has long been challenging. To address issues and regioselectivity, we introduced novel organoelectrocatalytic strategy enabling aryl-aryl dehydrogenative cross-coupling reactions. Using this approach, valuable were obtained up to 95% yields 97% enantiomeric excesses (ees), these compounds could be further applied as versatile ligands Detailed mechanistic studies...

Immobilization of chiral catalysts, which are composed precious metals and costly ligands, offers an economic environmental-friendly strategy. However, several challenges remain, including inferior activity selectivity compared to...

Asymmetric transfer hydrogenation (ATH) is an efficient and mild way to obtain chiral compounds. However, the toxic metal ions low turnover number (TON) in aqueous ATH limited further application. We reported a polystyrene‐covered mesoporous SiO2 supported Noyori’s Ru‐TsDPEN named Ru‐PCMS, consisting of inner silica core outer organic polystyrene layer, which could promote β‐keto esters afford various β‐hydroxy ester with excellent yields (up 99%) ee values 97%). It showed water stability...

Benefited by the accessible ynamido–lithium intermediates Ib from a Cu-catalyzed azide–alkyne cycloaddition in presence of stoichiometric amounts LiOH, mild and flexible three-component route to conjugated enyne scaffolds was successfully achieved via formal E-selective olefination strategy.

A tandem coupling-ketooxygenation reaction of readily accessible enediyne-carboxylic compounds with inner alkynes has been developed that utilizes the PdCl2/CuBr2 catalytic system under an O2 atmosphere and assembles a class isoindolinones o-acylbenzoic acids. The two oxygen atoms are regioselectively incorporated into enediyne units at 1- 6-positions from atmospheric molecular H2O, respectively, during present process. This study uncovered formal [4C + 2C] benzannulation-diketonization...

A traceless directing group assisted Co-catalyzed C(sp2)-H carbonylation of ortho-arylanilines for the synthesis free ( NH)-phenanthridinones in metal-based-oxidant-free fashion was accomplished. This protocol employs diisopropyl azodicarboxylate as CO source and oxygen sole oxidant, provides good yields with various functional tolerance. The methodology has been applied total PARP inhibitor PJ-34. Furthermore, kinetic isotopic effect experiments reveal C-H bond cleavage probably occurred...

The convergent synthesis of a class enediyne-imides as well their palladium-catalyzed branching cyclizations, which can be accomplished in two ways leading to set polysubstituted furo[2,3-b]pyridines upon using the N-tosyl carboxamide moiety an N,O-bisnucleophile, are presented.

An eco-friendly electrochemical synthesis of sulfinic esters from thiols and alcohols under mild reaction conditions has been developed.

A dehydrogenative [3 + 2] annulation reaction of aniline derivatives and alkenes has been developed via the ruthenium-electron catalytic systems for synthesis versatile indolines. Electricity is used as a sustainable oxidant to regenerate active Ru(II) catalyst promote H2 evolution. This protocol ecofriendly easy handle it uses simple undivided cell in mild conditions without employment metal oxidants.

A series of Mn(I) catalysts containing imidazole-based chiral PNN tridentate ligands with controllable ‘side arm’ groups have been established, enabling the inexpensive base-promoted asymmetric hydrogenation simple ketones outstanding activities (up to 8200 TON) and good enantioselectivities 88.5% ee). This protocol features wide substrate scope functional group tolerance, thereby providing easy access a key intermediate crizotinib.

An eco-friendly electrochemical C-3 formylation of indoles using Me₃N as a carbonyl donor in recyclable reaction medium has been developed.

The first example of manganese catalyzed asymmetric hydrogenation β-keto sulfones for the construction chiral β-hydroxy with up to 97% yield and ee.

A mild three-component synthetic approach to versatile 2-amino-1,4-dihydropyridines from terminal alkynes, sulfonyl azides, and N-sulfonyl-1-aza-1,3-butadienes was successfully developed relied on the in situ generation of metalated ynamide intermediates Ib achieve a formal inverse electron-demand hetero-Diels-Alder reaction. Experimental results suggest that alkali metal cations (Li(+) Cs(+) ions) might play critical role cycloaddition process.

A tunable copper-catalyzed azide–alkyne cycloaddition (CuAAC)-initiated multicomponent reaction strategy for the construction of 3-functionalized indolin-2-ones is reported. Upon controlling ring opening four-membered O-heterocyclic intermediates, this unique method enables divergent derivatization N-protected isatins to give three-component (3-CR) and four-component (4-CR) adducts, respectively.

Abstract The first example of CoCl 2 ‐catalyzed formal [5+2] oxidative annulation o ‐arylanilines with alkynes was developed, giving access to various important imine‐containing dibenzo‐[ b , d ]azepine scaffolds through sequential C−C/C−N bond formation. reaction employs catalytic amount manganese and oxygen as cooxidants, features a broad substrate scope. Preliminary mechanistic studies suggested that C−H activation is involved in the rate‐determining step. Moreover, both internal terminal...