Abstract A new method for CF 3 SO 2 Na‐based direct trifluoromethylthiolation of C(sp )H bonds has been developed. SSCF is generated in situ from cheap and easy‐to‐handle Na, the presence CuCl can be used electrophilic indoles, pyrroles, enamines. The extended to perfluoroalkylthiolation reactions using R f Na.

Despite diversity in reaction mechanisms, the palladium-catalyzed cyclization of 1,6-enyne generally proceeds a 5-exo manner. Herein, we report development Pd(0)-catalyzed hydroacyloxylative either 7-endo-trig or 6-exo-trig fashion when paired with an appropriate dihaloacetic acid reactant, such as F2HCCO2H and Cl2HCCO2H. Using combination Pd2(dba)3 chiral phosphine ligand, bearing 1,1-disubstituted alkene moiety readily gives highly enantiopure seven-membered heterocycles while those having...

A new strategy for the synthesis of 3,5-disubstituted phenols is established through one-pot Robinson annulation α,β-unsaturated ketones with α-fluoro-β-ketoesters followed by in situ dehydrofluorination and tautomerization. This method has been extended to polysubstituted applied preparation biologically active compounds.

A Pd-catalyzed atroposelective hydroamination has been developed for the efficient and rapid construction of a family axially chiral sulfonamides with wide functional group tolerance. Ortho-groups including undeveloped ester, ketone, nitro, Cl, F, OMe well-developed tBu, I, Br were all applicable in this transformation. Importantly, simple oxidation N,O-acetal moiety γ-addition to versatile atropoisomeric iminium ion enabled diversity-synthesis various valuable anilides. For example,...

Abstract A new method for CF 3 SO 2 Na‐based direct trifluoromethylthiolation of C(sp )H bonds has been developed. SSCF is generated in situ from cheap and easy‐to‐handle Na, the presence CuCl can be used electrophilic indoles, pyrroles, enamines. The extended to perfluoroalkylthiolation reactions using R f Na.

Central-to-axial chirality transfer via C–N single bond oxidation was first achieved as a versatile and conceptually distinct strategy to prepare new family of axially chiral heteroaromatic biaryl backbones P,N-ligands (named Quinoxalinaps) in gram scale. Two atropisomers Quinoxalinaps (ee >99%) were readily accessed from the same precursor enantiomer by simple dehydrogenative with MnO2 t-BuOOH under mild conditions. Phosphine could be introduced into ligands before or after control process....

Abstract 2,2‐Difluoro‐1,3‐diketones are introduced as gem ‐difluoroenolate precursors for the first example of an organocatalytic asymmetric aldol addition with N ‐benzylisatins to form 3‐difluoroalkyl‐3‐hydroxyoxindoles. magnified image

A family of axially chiral quinazolinone-based heterobiaryls were constructed with high levels enantiocontrol (up to 94% ee). Convergently, three different synthetic methods have been realized prepare these valuable compounds including central-to-axial chirality transfer, dynamic kinetic resolution, and phase-transfer catalysis. Importantly, novel P,N-ligands a π–π stacking can be derived from by exchange strategy or synthesized directly complementary catalysis using the inexpensive...

Reductive elimination of alkyl-PdII -O is a synthetically useful yet underdeveloped elementary reaction. Here we report that the combination an H-bonding donor [PyH][BF4 ] and AgNO3 additive under toluene/H2 O biphasic system can enable such step to form alkyl nitrate. This results in Pd0 -catalyzed asymmetric carbonitratations (Z)-1-iodo-1,6-dienes with (R)-BINAP as chiral ligand, affording nitrates up 96 % ee. Mechanistic studies disclose reaction consists oxidative addition catalyst vinyl...

Despite the widespread use of naphthamide atropisomers in biologically active compounds and asymmetric catalysis, few catalytic methods have succeeded enantioselective synthesis these compounds. Herein, a chiral Brønsted acid (CBA) catalysis strategy was developed for readily scalable dynamic kinetic resolution challenging ortho-formyl naphthamides with pyrrolylanilines. The axis atropisomeric amide stereogenic center were simultaneously established new family potential pyrrolopyrazine high...

Abstract Di‐ tert ‐butyl peroxide can smoothly promote the coupling of aryl halides with benzene derivatives without aid transition‐metal catalysts through a chain homolytic aromatic substitution mechanism in presence potassium ‐butoxide.

The highly stereoselective olefination reaction of α-fluoro-β-keto esters for the synthesis α-fluoro-α,β-unsaturated has been developed. combines nucleophilic addition, intramolecular and elimination in one step, as well provides a facile synthetic approach to which are important units many biologically active compounds useful precursors variety functional-group transformations.

Background: Development of straightforward and atom/step-economic approaches for new C-C bond formation from readily available starting materials is one the fundamental goals in area chemical synthesis. Among these strategies, Pd-catalyzed allylic alkylation represents powerful synthetic tools has been widely utilized organic The direct use alcohol itself instead its derivatives, such as carbonates, amines, acetates, halides, π-allyl fragment source presents higher atom-/step-economy much...

Abstract A phosphine‐catalyzed (3+2) annulation of 4‐acetoxy allenoate and aldimine with the assistance AgF is described. The success this reaction hinges on metathesis between enolate‐phosphonium zwitterion AgF, leading to a key intermediate comprising silver enolate fluorophosphorane P(V)‐moiety. former able undergo Mannich aldimine, whereas latter initiates cascade sequence AcO‐elimination/aza‐addition, thus furnishing P(III)/P(V) catalysis. By taking advantage enolate, preliminary...

Phosphine catalysis generally relies on the potential of carbanion-phosphonium zwitterions that are generated via nucleophilic addition phosphine catalyst to electrophilic reactants. Consequently, structural modification using distinct reactants has emerged as a prominent strategy enhance diversity. Herein, we present an alternative utilizes AgF additive expand catalysis. We find can readily transform canonical carbanion–phosphonium zwitterion into silver enolate–fluorophosphorane...

A novel process involving Grignard-reagent-promoted desulfonylation/intramolecular coupling of readily available α-fluoro-α,β-unsaturated-(2-pyridyl)sulfones was realized that provided a series polysubstituted 2-(1-fluorovinyl)pyridines in good yields. The intrinsic coordination between pyridine and Mg(II) along with the "negative fluorine effect" substrates should play key role for smooth transformation absence transition-metal catalysts.

A novel intramolecular Smiles rearrangement of α-fluoro-β-keto-pyrimidylsulfones (usually used as a carbon nucleophile) was developed, providing versatile avenue for synthesis tri/tetra-substituted monofluorinated pyrimidyl enol ethers. Among these, diverse (Z)-monofluorovinylsulfones and sulfinates were efficiently assembled by adding extra electrophile fine-tuning reaction conditions. The process is triggered keto–enol tautomerism from oxyanion to pyrimidine 2-carbon, completely different...

A family of axially chiral azepine-containing seven-membered cyclic P,N-ligands (named Indole-azepinap) have been prepared by using l-alanine as an original chirality source. The direct chromatographic separation two diastereomeric phosphine oxides on silica gel enabled these ligands to be easy available, allowing further structural and electronic modifications. Preliminary application Indole-azepinaps has demonstrated in a Pd-catalyzed asymmetric allylic alkylation with high yields moderate...

Reported is a unique chemoselectivity approach to base-promoted defluorinative and Cu(i)-catalyzed aerobic oxidative non-defluorinative [5 + 1] condensation aromatizations of simple unsaturated ketones with ammonium salts via Meisenheimer-type nitrogen anion radical intermediates. The CuBr/O2 catalysis provides straightforward diverse 3-fluoropyridines in high yields. synthetic utility the strategy highlighted by concise synthesis several F-modified bioactive compounds.

Open AccessCCS ChemistryRESEARCH ARTICLE1 Jun 2021Fluorine Effects for Tunable C–C and C–S Bond Cleavage in Fluoro-Julia–Kocienski Intermediates Lei Kang†, Yongjia Lin†, Zeng Gao, Jinlong Zhang, Huameng Yang, Qian, Qian Peng Gaoxi Jiang Kang† State Key Laboratory Oxo Synthesis Selective Oxidation, Center Excellence Molecular Synthesis, Suzhou Research Institute of LICP, Lanzhou Chemical Physics (LICP), Chinese Academy Sciences, 730000 Element-Organic Chemistry, College Nankai University,...

Abstract Two approaches involving intramolecular and intermolecular cyclization, respectively, have been developed for the direct practical construction of a series important benzo[f]pyrrolo[1,2-a][1,4]azepines by using Brønsted acid catalysts. Upon catalysis TsOH, dehydroxylation/ring closure 3-hydroxy-2-[2-(1H-pyrrol-1-yl)benzyl]isoindolin-1-ones provided various racemic in high yields. Furthermore, enantioenriched were also obtained chiral phosphoric catalyzed addition...

Abstract A novel process involving base-catalyzed intramolecular defluorination/O-arylation of readily available α-fluoro-β-one-sulfones was realized and provided a series 3-fluoro-1,4-oxathiine 4,4-dioxide derivatives in good to excellent yields. Unlike traditional defluorination reactions with stoichiometric base as the deacid reagent, this is triggered by catalytic amount (TMG: tetramethylguanidine) molecular sieves serve both an adsorbent remove HF acid activator assist C–F bond cleavage.