56079-45-9

Upstream product

• 22700-73-8 1-(dimethylamino)-4,4-dimethylpentan-3-one 
• 100-52-7 benzaldehyde 
• 72972-04-4 1-(1-tert-butyl-vinyl)-pyrrolidine 
• 70-11-1 α-bromoacetophenone 
• 64723-95-1 pinacolone enolate anion 
• 28531-58-0 (2-oxo-2-phenylethyl)mercury chloride 
• 3282-30-2 pivaloyl chloride 
• 142896-16-0 (E)-1-Phenyl-3-(tri-n-butylstannyl)-2-propen-1-one 
• 17795-68-5 (C₄H₉)3SnOC(t-C₄H₉)CH₂ 
• 131799-53-6 N-(2-Chloro-1-phenyl-1-ethylidene)isopropylamine 
• 72084-30-1 1-triethylgermyloxy-1-tert-butylethene 
• 66324-10-5 tert-butyldimethyl(1-phenylvinyloxy)silane 
• 22502-84-7 4-(1-t-butylethenyl)morpholine 
• 71953-55-4 2-phenyl-4-tert-butyloxazolin-5(4H)-one 

Downstream Products

• 199596-50-4 5-t-butyl-8-phenylindolizine 
• 199596-55-9 8-phenylindolizine 

Relevant academic research and scientific papers

Generation of Cation Radicals from Enamines and Their Reactions with Olefins

Cation radicals of enamines, generated by the oxidation with CeIV compounds, react with electron-rich olefins to give the addition products.The formal α-alkylation of formylacetate is realized by the reaction of 3-(1-pyrrolidinyl)propenoate and

Kinetic Resolution of Allylic Alcohol with Chiral BINOL-Based Alkoxides: A Combination of Experimental and Theoretical Studies

The development and characterization of enantioselective catalytic kinetic resolution of allylic alcohols through asymmetric isomerization with chiral BINOL derivatives-based alkoxides as bifunctional Br?nsted base catalysts were described in the study. A number of chiral BINOL derivatives-based alkoxides were synthesized, and their structure-enantioselectivity correlation study in asymmetric isomerization identified a promising chiral Br?nsted base catalyst, which afforded various chiral secondary allylic alcohols (ee up to 99%, S factor up to >200). In the mechanistic study, alkoxide species were identified as active species and the phenol group of BINOL largely affected the high reactivity and enantioselectivity via hydrogen bonding between the chiral Br?nsted base catalyst and substrates. The strategy is the first successful synthesis strategy of various chiral secondary allylic alcohols through enantioselective transition-metal-free base-catalyzed isomerization. The applicability of the strategy had been demonstrated by the synthesis of the bioactive natural product (+)-veraguensin.

Synthesis of 1,4-Dicarbonyl Compounds from Silyl Enol Ethers and Bromocarbonyls, Catalyzed by an Organic Dye under Visible-Light Irradiation with Perfect Selectivity for the Halide Moiety over the Carbonyl Group

We report the visible-light-induced radical coupling reaction of silyl enol ethers with α-bromocarbonyl compounds to give 1,4-dicarbonyls. The reaction was effectively accelerated using an inexpensive organic dye (eosin Y) as a photoredox catalyst. 1,4-Dicarbonyl compounds alone were afforded, without the generation of carbonyl adducts of the α-halocarbonyls, which are usually generated in the presence of fluoride anions or Lewis acids. A variety of silyl enol ethers, α-bromoketones, α-bromoesters, and α-bromoamides were applied to this system to produce the coupling compounds.

2,5-Disubstituted furans from 1,4-alkynediols

1,4-Alkynediols serve as readily available starting materials for isomerisation to 1,4-diketones, which can be converted in situ into the corresponding furans by acid-catalysed dehydration. A range of 2,5-disubstituted furans was prepared using the ruthenium-based catalyst Ru(PPh3)3(CO)H2 with Xantphos at 1 mol % loading.

Zinc-mediated chain extension reaction of 1,3-diketones to 1,4-diketones and diastereoselective synthesis of trans-1,2-disubstituted cyclopropanols

A variety of 1,3-diketones can be efficiently converted into the corresponding 1,4-diketones and trans-1,2-disubstituted cyclopropanols by using organozinc species in one-pot reactions. It was found that 2.3 equiv of CF 3CO2ZnCH2I was effective to give the corresponding chain-extended products in 44-85% yields, while a mixture of organozinc species formed from 4.0 equiv of Et2Zn, 2.0 equiv of CF3CO2H, and 4.0 equiv of CH2I2 resulted in the formation of trans-1,2-disubstituted cyclopropanols with quite good yields and diastereoselectivity.

Chemistry of ketone α,β-dianions. Acylation reactions of dianion cuprates by acid chlorides

The cross-coupling reaction of dianion cuprates, generated from ketone α,β-dianions and copper salts, with acid chlorides, was studied. The reaction gave good to moderate yields of unsymmetrical 1,4-diketones. The consecutive treatment of a dianion cuprate with cyclohexanecarbonyl chloride and methyl iodide or two different acid chlorides gave 2-methyl-substituted 1,4-diketone or triketone, respectively.

Cross-coupling reaction of α-chloroketones and organotin enolates catalyzed by zinc halides for synthesis of γ-diketones

The reaction of tin enolates 1 with α-chloro- or bromoketones 2 gave γ-diketones (1,4-diketones) 3 catalyzed by zinc halides. In contrast to the exclusive formation of 1,4-diketones 3 under catalytic conditions, uncatalyzed reaction of 1 with 2 gave aldol-type products 4 through carbonyl attack. NMR study indicates that the catalyzed reaction includes precondensation between tin enolates and α-haloketones providing an aldol-type species and their rearrangement of the oxoalkyl group with leaving halogen to produce 1,4-diketones. The catalyst, zinc halides, plays an important role in each step. The carbonyl attack for precondensation is accelerated by the catalyst as Lewis acid and the intermediate zincate promotes the rearrangement by releasing oxygen and bonding with halogen. Various types of tin enolates and α-chloro and bromoketones were applied to the zinc-catalyzed cross-coupling. On the other hand, the allylic halides, which have no carbonyl moiety, were inert to the zinc-catalyzed coupling with tin enolates. The copper halides showed high catalytic activity for the coupling between tin enolates 1 and organic halides 7 to give γ,δ-unsaturated ketones 8 and/or 9. The reaction with even chlorides proceeded effectively by the catalytic system.

A Convenient Synthesis of 8-Substituted Indolizines as Precursors to 5-Substituted Cycl{3.2.2}azine Derivatives

The synthesis of 8-substituted indolizines is described via a two step process in which a 1,4-diketone, containing a tert-butyl group, is cyclocondensed with a trialkylsilyl protected pyrrole to provide 5,8-disubstituted indolizines in higher yields than the identical reaction with unprotected pyrrole. Cleavage of the tertbutyl group from the indolizine 5-position, by treatment with 85% phosphoric acid, provides 8-substituted indolizines in good yields. Treatment of 8-substituted indolizines with dimethyl acetylenedicarboxylate, in the presence of palladium-on-carbon, provides novel 5-substituted cycl{3.2.2} derivatives.

NMR Studies of Five-Coordinate Tin Enolate: An Efficient Reagent for Halo Selective Reaction toward α-Halo Ketone or α-Halo Imine

NMR studies of tin enolates 1, in the presence of HMPA, revealed the presence of a five-coordinate O-stannyl enolate 1(h) which contributes to upfield shifts of Sn peaks in the 119Sn NMR spectrum and increased coupling constants J(119Sn-13C), compared wit

Palladium-Catalyzed Reductive Coupling of Acid Chlorides with β-Stannyl Enones: Synthesis of 1,4-Diketones and Mechanistic Aspects

The palladium-catalyzed coupling of acid chlorides with (E)-1,2-bis(tri-n-butylstannyl)ethene or β-stannyl enones gives butane-1,4-diones directly by reduction of the intermediate enedicarbonyl intermediate.The double bond conjugated with a single carbonyl group was not significantly reduced.The generality of the method is illustrated by two syntheses of the 1,4-diketone ipomeanine.By performing the reaction at lower temperatures, α,β-unsaturated 1,4-diketones can also be prepared.The reduction of the intermediate α,β-unsaturated 1,4-diketones probably proceeds by insertion of a palladium hydride, formed in situ by reaction of a Pd(II) complex with Bu3SnCl, followed by hydrolysis of the intermediate palladium enolate.