低价钛诱导的芳香邻二酮及α-羟基酮的还原偶联反应

Treatment of aromatic 1 , 2-diketones or aromatic a-hydroxy ketones with an activated low-valent titanium reagent, prepared by reduction of TiCl3·1/3AlCl3 with a Zn-Cu reagent, gave an intermolecular coupling reaction leading to the (Z)-1, 2.3.4-tetraaryl-2-butenes. Apossible coupling reaction process was proposed for the aromatic a-hydroxy ketones.     

A One-Pot Reductive Acetylation of Aldehydes and Ketones

Sodium borohydride reduction of saturated aliphatic and aromatic aldehydes and ketones in ethyl acetate at reflux is a facile route for one-pot preparation of acetates from such carbonyl precursors.     

Enantioselective Nickel-Catalyzed anti-Arylmetallative Cyclizations onto Acyclic Ketones

Domino reactions involving nickel-catalyzed additions of (hetero)arylboronic acids to alkynes, followed by cyclization of the alkenylnickel intermediates onto tethered acyclic ketones to give chiral tertiary-alcohol-containing products in high enantioselectivities, are described. The reversible E/Z isomerization of the alkenylnickel intermediates enables overall anti-arylmetallative cyclization to occur. The ring system of the products are substructures of certain diarylindolizidine alkaloids.     

A Simple Alkylative 1,2-Carbonyl Transposition of Cyclohexenones

Acid catalysed dehydration of the diols 5 , derived from the cyclohexenone 3 affords mixtures of 8 and 11 . The product ratio 8/11 , although strongly dependent on both the reaction conditions and the substituent R, is independent of the diol configuration; this indicates a cationic intermediate 6 . Conditions were found, which allow the sequence A → B → C → D (Scheme 2) to be applied to the syntheses of the enones 8, 21 and 25 in fair to good yields from the corresponding cyclohexenones 3, 18 and 22 .     

Sequence-Dependent Stereodivergent Allylic Alkylation/Fluorination of Acyclic Ketones

The stereodivergent iridium-catalyzed allylic alkylation and fluorination of acyclic ketones is described. α-Pyridyl-α-fluoroketones with vicinal tertiary and quaternary stereocenters were obtained in moderate to excellent yields and stereoselectivities. Distinct from known stereodivergent synthesis, for which two different chiral catalysts are required in general, herein we report a sequence-dependent stereodivergent synthesis. With only a single chiral Ir catalyst, all four possible stereoisomers of the products were prepared from the same starting materials by simply adjusting the sequence of asymmetric allylic alkylation and fluorination and varying the absolute configuration of the Ir catalyst.     

Reductive Chlorination and Bromination of Ketones via Trityl Hydrazones

A method is presented for the direct transformation of a ketone to the corresponding reduced alkyl chloride or bromide. The process involves the reaction of a ketone trityl hydrazone with tBuOCl to give a diazene which readily collapses to the α‐chlorocarbinyl radical, reduction of which by a hydrogen atom source gives the alkyl chloride product. The use of N‐bromosuccinimide provides the corresponding alkyl bromide. This unique transformation provides a reductive halogenation that complements Barton's redox‐neutral vinyl halide synthesis.     

低价钛引起的邻硝基苯甲酰胺与酮的还原成环反应

报道了TiCl₄-Sm体系引起的邻硝基苯甲酰胺与酮的反应.研究发现,邻硝基苯甲酰胺与酮还原成环生成1,2-二氢喹唑啉-4(3H)-酮.产物的结构通过元素分析、IR、¹HNMR谱和单晶X射线衍射法确定.     

A Novel Reductive Cyclization of o-Nitrobenzamides and Ketones Promoted by Low-valent Titanium Reagent

A short and facile synthesis of a series of 1,2-dihydroquiazolin-4(3H)-ones was accomplished in good yields via novel reductive cyclization of o-nitrobenzamides with ketones promoted by TiCI4/Zn system. The structure was established on the basis of elemental analysis, IR,^1H NMR and confirmed by a single-crystal X-ray diffraction analysis. This method has the advantages of easily accessible starting materials, convenient manipulation and moderate to high yields.     

Air Stable Iridium Catalysts for Direct Reductive Amination of Ketones

Half-sandwich iridium complexes bearing bidentate urea-phosphorus ligands were found to catalyze the direct reductive amination of aromatic and aliphatic ketones under mild conditions at 0.5 mol % loading with high selectivity towards primary amines. One of the complexes was found to be active in both the Leuckart–Wallach (NH₄CO₂H) type reaction as well as in the hydrogenative (H₂/NH₄AcO) reductive amination. The protocol with ammonium formate does not require an inert atmosphere, dry solvents, as well as additives and in contrast to previous reports takes place in hexafluoroisopropanol (HFIP) instead of methanol. Applying NH₄CO₂D or D₂ resulted in a high degree of deuterium incorporation into the primary amine α-position.     

Sequence‐Dependent Stereodivergent Allylic Alkylation/Fluorination of Acyclic Ketones

The stereodivergent iridium‐catalyzed allylic alkylation and fluorination of acyclic ketones is described. α‐Pyridyl‐α‐fluoroketones with vicinal tertiary and quaternary stereocenters were obtained in moderate to excellent yields and stereoselectivities. Distinct from known stereodivergent synthesis, for which two different chiral catalysts are required in general, herein we report a sequence‐dependent stereodivergent synthesis. With only a single chiral Ir catalyst, all four possible stereoisomers of the products were prepared from the same starting materials by simply adjusting the sequence of asymmetric allylic alkylation and fluorination and varying the absolute configuration of the Ir catalyst.     

Nickel-Catalyzed Asymmetric Reductive 1,2-Carboamination of Unactivated Alkenes

Starting from diverse alkene-tethered aryl iodides and O-benzoyl-hydroxylamines, the enantioselective reductive cross-electrophilic 1,2-carboamination of unactivated alkenes was achieved using a chiral pyrox/nickel complex as the catalyst. This mild, modular, and practical protocol provides rapid access to a variety of β-chiral amines with an enantioenriched aryl-substituted quaternary carbon center in good yields and with excellent enantioselectivities. This process reveals a complementary regioselectivity when compared to Pd and Cu catalysis.     

Reduction of Carbon Oxides by an Acyclic Silylene: Reductive Coupling of CO

Reactions of a boryl‐substituted acyclic silylene with carbon dioxide and monoxide are reported. The former proceeds through oxygen atom abstraction, generating CO (with rearrangement of the putative silanone product through silyl‐group transfer). The latter is characterized by reductive coupling of CO to give an ethynediolate fragment, which undergoes formal insertion into the Si?B bond. The net conversion of carbon dioxide with two equivalents of silylene offers a route for the three‐electron reduction of CO₂ to [C₂O₂]^2?.     

Diastereo- and Enantioselective Reductive Aldol Addition of Vinyl Ketones via Catalytic Hydrogenation

An overview of studies on hydrogenative reductive aldol addition is presented. By simply hydrogenating enones in the presence of aldehydes at ambient temperature and pressure, aldol adducts are generated under neutral conditions in the absence of any stoichiometric byproducts. Using cationic rhodium complexes modified by tri(2-furyl)phosphine, highly syn-diastereoselective reductive aldol additions of vinyl ketones are achieved. Finally, using novel monodentate TADDOL-like phosphonite ligands, the first highly diastereo- and enantioselective reductive aldol couplings of vinyl ketones were devised. These studies, along with other works from our laboratory, demonstrate that organometallics arising transiently in the course of catalytic hydrogenation offer byproduct-free alternatives to preformed organometallic reagents employed in classical carbonyl addition processes.     

Synthesis of Hydrophenanthbene Derivatives Related to Diterpenes Involving Reductive Methylation of Aromatic Ketones

The tricyclic ketones 13 and 14, prepared from naphthalene and 2-methoxynaphthalene respectively, were subjected to reductive methylation in anhydrous ammonia to provide the β, γ -unsaturated ketones 16 and 17 in high yield which were stereoselectively converted into the A/B trans-fused compounds 3 and 4 respectively.     

Reductive metalation of 1,2-diaryl-substituted ethenes: synthetic applications

Reduction of 1,2-diaryl-substituted ethenes with Na metal in dry THF allowed easy access to a variety of 1,2-diaryl-1,2-disodiumethanes. These diorganometallic intermediates were elaborated into the corresponding 1,2-diarylethanes (aqueous work up), or cycloalkylated with 1,3-dichloropropanes. The last reaction led to a highly diastereoselective synthesis of trans-1,2-diaryl-substituted cyclopentanes.     

Reductive Amination of Aldehydes and Ketones with 2-(Tributylamino)-ethoxyborohydride

A new ionic liquid is presented as a medium and reducing agent for the reductive amination of aldehydes and ketones.     

Reductive Amination of Aldehydes and Ketones with 2-(Tributylamino)-ethoxyborohydride

Summary. A new ionic liquid is presented as a medium and reducing agent for the reductive amination of aldehydes and ketones.     

Directed Asymmetric Nickel-Catalyzed Reductive 1,2-Diarylation of Electronically Unactivated Alkenes

Transition-metal catalyzed intermolecular 1,2-diarylation of electronically unactivated alkenes has emerged as an extensive research topic in organic synthesis. However, most examples are mainly limited to terminal alkenes. Furthermore, transition-metal catalyzed asymmetric 1,2-diarylation of unactivated alkenes still remains unsolved and is a formidable challenge. Herein, we describe a highly efficient directed nickel-catalyzed reductive 1,2-diarylation of unactivated internal alkenes with high diastereoselectivities. More importantly, our further effort towards enantioselective 1,2-diarylation of the unactivated terminal and challenging internal alkenes is achieved, furnishing various polyarylalkanes featuring benzylic stereocenters in high yields and with good to high enantioselectivities and high diastereoselectivities. Interestingly, the generation of cationic Ni-catalyst by adding alkali metal fluoride is the key to increased efficiency of this enantioselective reaction.