Rhodium-Catalyzed Synthesis of Trifluoromethyl-Containing Allylic Alcohols Via -Alkenyl Transfer with High Stereochemistry Retention.

Herein, we report the rhodium-catalyzed -alkenyl transfer from tertiary allylic alcohols to aryl trifluoromethyl ketones, which provided an efficient way of preparation of trifluoromethyl-containing -allylic alcohols via β--alkenyl elimination. The key -alkenyl-rhodium species were generated with a high degree of stereochemical retention. This reaction featured a broad substrate scope and good functional tolerance and would offer a fascinating approach for the synthesis of -alkenes.

P2RY6 deletion promotes UVB-induced skin carcinogenesis by activating the PI3K/AKT signal pathway.

Our previous research has demonstrated that P2RY6 functions as an oncogene in DMBA/TPA-induced two-stage chemical skin carcinogenesis in mice. However, considering that human skin cancer is predominantly attributed to UV radiation from sunlight, additional investigations are needed to elucidate the role of P2RY6 in UVB-induced skin carcinogenesis. Surprisingly, we found that P2ry6-deficient mice exhibited marked promotion to UVB-induced skin papilloma formation compared with wild-type mice, suggesting its tumor-suppressive role in UVB-induced skin cancer.

Synthesis of 1,2,4,5-tetra-substituted benzenes copper-catalyzed dimerization of γ,δ-unsaturated ketones.

An efficient cyclization for the synthesis of 1,2,4,5-tetra-substituted benzenes copper catalyzed dimerization of γ,δ-unsaturated ketones has been described. This one-pot procedure employs the γ,δ-unsaturated ketones as the sole substrate with multiple C-C bond formation. This protocol features broad substrate scope and provides a facile and robust method to construct polysubstituted benzene derivatives under mild conditions.

N1-methylnicotinamide impairs gestational glucose tolerance in mice.

N1-methylnicotinamide (MNAM), a product of methylation of nicotinamide through nicotinamide N-methyltransferase, displays antidiabetic effects in male rodents. This study aimed to evaluate the ameliorative potential of MNAM on glucose metabolism in a gestational diabetes mellitus (GDM) model. C57BL/6N mice were fed with a high-fat diet (HFD) for 6 weeks before pregnancy and throughout gestation to establish the GDM model.

Rhodium(III)-catalyzed three-component C(sp)-H activation for the synthesis of amines.

Rhodium-catalyzed three-component C-H bond activation of aromatics with amides and aldehydes to synthesize amines was established. The addition of copper was found to be essential to ensure the high reactivity. The mechanistic studies indicated that key intermediates formed by the transmetallization between rhodium and copper could further promote the addition between 2-(pyridin-2-yl)-phenyl-metal species and imines.

Copper-Catalyzed Aza-Benzyl Transfer Michael Addition via C-C Bond Cleavage.

A non-noble Cu-catalyzed transfer aza-benzyl Michael addition via the C-C bond cleavage of aza-benzyl alcohols has been disclosed. The unstrained C(sp)-C(sp) bond of an alcohol was selectively cleaved. This aza-benzyl transfer strategy provides a selective and environmentally benign approach for the C-alkylation of α,β-unsaturated carbonyl compounds that employs readily available alcohols as carbon nucleophiles and is characterized by a wide range of substrates and good to excellent yields.

Sulfonylation of Propargyl Alcohols with Sulfinamides for the Synthesis of Allenyl Sulfones.

A regio- and chemoselective sulfonylation of propargyl alcohols with sulfinamides in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) was developed. It provided straightforward and mild access to multi-substituted allenyl sulfones by using sulfinamides as the sulfonyl sources. This transformation was promoted by HFIP and did not require any catalysts or oxidants, which allowed for the successful conversion of various tertiary and secondary propargyl alcohols into allenyl sulfones in high yields.

Ruthenium-Catalyzed 1,3-Aryl Redox Isomerization of Allylic Alcohols.

The isomerization of allylic alcohols to the corresponding carbonyl compounds is a well-established reaction in organic synthesis. However, 1,3-carbon migration is a quite challenging field, and thus transformation has remained elusive until now. Herein, we present the ruthenium-catalyzed intramolecular 1,3-aryl migrative isomerization, which provides a mild and environmentally friendly method to synthesize various ketones with high step- and atom-economy and broad substrate scope.

Silver-Catalyzed 1,3-Aza-Benzyl Migration of Allyl Alcohol.

Carbon migration of alkenyl alcohols has been recognized as an increasingly viable methodology in organic synthesis. Herein, we disclose a silver-catalyzed 1,3-aza-benzyl migration of allyl alcohols by utilizing chelation-assisted selective cleavage of an unstrained C(sp)-C(sp) bond. This approach provides an available, efficient, high atom-economic, and environmentally benign procedure, leading to alkylation products with broad substrate scopes and excellent yields.

Alkynyl Borrowing: Silver-Catalyzed Amination of Secondary Propargylic Alcohols via C(sp)-C(sp) Bond Cleavage.

The silver-catalyzed alkynyl borrowing amination of secondary propargyl alcohols via C(sp)-C(sp) bond cleavage has been developed. This new strategy was based on the β-alkynyl elimination of propargyl alcohols and alkynyl as the borrowing subject. This alkynyl borrowing amination featured high atom economy, wide functional group tolerance, and high efficiency.

1,1,1,3,3,3-Hexafluoro-2-propanol (HFIP)-Assisted Catalyst-Free Sulfonation of Allylic Alcohols with Sulfinyl Amides.

A highly regioselective and catalyst-free sulfonation of allylic alcohols with sulfinyl amides has been realized. Such a mix-and-go procedure provides a convenient approach to synthetically various allylic sulfones under mild reaction conditions. Furthermore, this novel reaction shows ample substrate scope and outstanding functional group tolerance and could also be scaled-up.

Tanshinone Inhibits NSCLC by Downregulating AURKA Through Let-7a-5p.

Lung cancer is the most deadly malignancy in the last decade, accounting for about 1.6 million deaths every year globally. Tanshinone is the constituent of ; it has been found that they influence tumorigenesis.

Cyano-borrowing: titanium-catalyzed direct amination of cyanohydrins with amines and enantioselective examples.

The direct amination of cyanohydrins with amines via a catalytic cyano-borrowing reaction was developed. The transformation features broad substrate scope, excellent functional group compatibility, and very mild and simple operations. Moreover, a titanium catalyst supported by quinine and (S)-BINOL ligands enabled an asymmetric cyano-borrowing reaction with moderate to high enantioselectivity.

Titanium-Catalyzed Cyano-Borrowing Reaction for the Direct Amination of Cyanohydrins with Ammonia.

α-Aminonitrile was an important building block in natural products and key intermedia in organic chemistry. Herein, the direct amination of cyanohydrins with the partner of ammonia to synthesis N-unprotected α-aminonitriles is developed. The reaction proceeds via titanium-catalyzed cyano-borrowing reaction, which features high atom economy and simple operation.

Cyano-borrowing reaction: nickel-catalyzed direct conversion of cyanohydrins and aldehydes/ketones to β-cyano ketone.

A direct nickel-catalyzed, high atom- and step-economical reaction of cyanohydrins with aldehydes or ketones an unprecedented "cyano-borrowing reaction" has been developed. Cleavage of the C-CN bond of cyanohydrins followed by aldol condensation and conjugate addition of cyanide to α,β-unsaturated ketones proceeded to deliver a range of racemic β-cyano ketones with good to high yields. The practical procedure with the use of a commercial and less-toxic CN source bodes well for wide application of this protocol.

Rhodium-Catalyzed Enantioconvergent Isomerization of Homoallylic and Bishomoallylic Secondary Alcohols.

We present herein an unprecedented enantioselective isomerization of homoallylic and bishomoallylic secondary alcohols, catalyzed by a commercially available rhodium-complex and a base. This catalytic redox-neutral process provides an effective access to chiral ketones in high efficiency and enantioselectivity, without the use of any stoichiometric reagent or generation of any waste. For the reaction of homoallylic alcohols, this system achieved not only a stereoconvergent access to chiral ketones bearing a β-stereocenter (up to 95%, 86% ee) but also a concomitant oxidative kinetic resolution of the alcohol substrates (S > 20).

Pd-Catalyzed Enantioselective [6+4] Cycloaddition of Vinyl Oxetanes with Azadienes to Access Ten-Membered Heterocycles.

We report herein the first enantioselective cycloaddition of vinyl oxetanes, the reaction of which with azadienes provided unprecedented access to ten-membered heterocycles through a [6+4] cycloaddition. By using a commercially available chiral Pd-SIPHOX catalyst, a wide range of benzofuran- as well as indole-fused heterocycles could be accessed in excellent yield and enantioselectivity. A unique Lewis acid induced fragmentation of these ten-membered heterocycles was also discovered.

Divergent reactivities in fluoronation of allylic alcohols: synthesis of -fluoroalkenes carbon-carbon bond cleavage.

An unconventional cleavage of an unstrained carbon-carbon bond in allylic alcohols can be induced by the use of -fluorobenzenesulfonimide (NFSI) under catalyst-free conditions. By using this simple procedure, a wide range of functionalized -fluoroalkenes can be accessed in high yield and selectivity from cyclic and acyclic allylic alcohols.

Rhodium-Catalyzed Enantioselective Isomerization of Secondary Allylic Alcohols.

The first catalytic enantioselective isomerization of secondary allylic alcohols to access ketones with a α-tertiary stereocenter is presented. The racemic allylic alcohol substrates can be converted to the enantioenriched ketone products in a stereoconvergent fashion. The use of commercially available catalysts and mild reaction conditions makes this an attractive method in stereoselective synthesis.

Highly enantioselective synthesis of chiral cyclic allylic amines via Rh-catalyzed asymmetric hydrogenation.

Highly regioselective and enantioselective asymmetric hydrogenation of cyclic dienamides catalyzed by an Rh-DuanPhos complex has been developed, which provides a readily accessible method for the synthesis of chiral cyclic allylic amines in excellent enantioselectivities (up to 99% ee). The products are valuable chiral building blocks and could be easily transformed to multisubstituted cyclohexane derivatives.

exo-Selective construction of spiro-[butyrolactone-pyrrolidine] via 1,3-dipolar cycloaddition of azomethine ylides with α-methylene-γ-butyrolactone catalyzed by Cu(I)/DTBM-BIPHEP.

An expedient access to optically active spiro-[butyrolactone-pyrrolidine] was successfully developed via an unprecedented Cu(I)-catalyzed exo-selective 1,3-DC of azomethine ylides with α-methylene-γ-butyrolactone, which exhibited high diastereoselectivity (>98 : 2), excellent enantioselectivity (96->99% ee) and a broad substrate scope under mild conditions.

Catalytic enantioselective desymmetrization of meso cyclic anhydrides via iridium-catalyzed hydrogenation.

A novel method to desymmetrize meso-anhydrides into lactones via asymmetric hydrogenation catalyzed by the Ir-C3*-TunePhos complex has been developed. Various chiral lactones were synthesized with full conversion and excellent enantioselectivity under high reaction temperature.

A facile access to enantioenriched isoindolines via one-pot sequential Cu(I)-catalyzed asymmetric 1,3-dipolar cycloaddition/oxidation [corrected].

Facile access to enantioenriched isoindolines bearing a quaternary stereogenic center and a tertiary stereogenic center was successfully developed via highly efficient Cu(I)/(S,Rp)-PPFOMe-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine ylide with quinone derivatives followed by silica-gel-promoted oxidation [corrected] in a one-pot reaction protocol. The present catalytic system exhibited high diastereoselectivity, excellent enantioselectivity, and a broad substrate scope under mild conditions.

Stereoselective construction of spiro(butyrolactonepyrrolidines) by highly efficient copper(I)/TF-BiphamPhos-catalyzed asymmetric 1,3-dipolar cycloaddition.

Pyrrole into one: The catalytic asymmetric 1,3-dipolar cycloaddition of cyclic aldimino esters has been accomplished for the first time, enabling facile access to spiro(butyrolactonepyrrolidines) containing one spiro quaternary center and three tertiary stereogenic centers (see scheme). The catalytic system performs well with a broad range of substrates, furnishing synthetically useful adducts in high yields, with excellent diastereo- and enantioselectivities under mild conditions.