38376-73-7

Upstream product

• 94-02-0 ethyl 3-oxo-3-phenylpropionate 
• 591-97-9 1-chloro-2-butene 
• 4784-77-4 (E/Z)-crotyl bromide 
• 17851-98-8 1-phenyl-1-(tributylstannyloxy)ethene 
• 542-72-3 (E)-but-2-en-1-ol 
• 532-27-4 1-chloroacetophenone 
• 106-99-0 buta-1,3-diene 
• 98-86-2 acetophenone 
• 13735-81-4 1-styrenyloxytrimethylsilane 
• 4088-60-2 cis-2-buten-1-ol 
• 56139-59-4 4-oxo-4-phenyl-butyraldehyde 
• 1530-32-1 ethyltriphenylphosphonium bromide 
• 15482-43-6 cis-(2-ethenylcyclopropyl)(phenyl)methanone 
• 21575-75-7 ethyl 2-(but-2-yn-1-yl)-3-oxo-3-phenylpropanoate 

Downstream Products

• 59321-58-3 1-Phenyl-4-hexen-1-ol 
• 139909-12-9 6-Chloro-6-phenyl-2-hexene 
• 182144-39-4 C₁₂H₁₅O 

Relevant academic research and scientific papers

Selective Synthesis of Z-Silyl Enol Ethers via Ni-Catalyzed Remote Functionalization of Ketones

We report a remote functionalization strategy, which allows the Z-selective synthesis of silyl enol ethers of (hetero)aromatic and aliphatic ketones via Ni-catalyzed chain walking from a distant olefin site. The positional selectivity is controlled by the directionality of the chain walk and is independent of thermodynamic preferences of the resulting silyl enol ether. Our mechanistic data indicate that a Ni(I) dimer is formed under these conditions, which serves as a catalyst resting state and, upon reaction with an alkyl bromide, is converted to [Ni(II)-H] as an active chain-walking/functionalization catalyst, ultimately generating a stabilized η3-bound Ni(II) enolate as the key selectivity-controlling intermediate.

Water-Accelerated Nickel-Catalyzed α-Crotylation of Simple Ketones with 1,3-Butadiene under pH and Redox-Neutral Conditions

We report a nickel/NHC-catalyzed branched-selective α-crotylation of simple ketones using 1,3-butadiene as the alkylation agent. This reaction is regioselective and operated under pH and redox-neutral conditions. Water was used as the sole additive, which significantly accelerates the transformation.

Pd-catalyzed domino carbonylative-decarboxylative allylation: An easy and selective monoallylation of ketones

In the presence of an allyl alcohol, α-chloroacetophenones undergo an allyloxycarbonylation reaction followed by in situ decarboxylative allylation to selectively afford the corresponding monoallylated ketones via a Pd-catalyzed domino sequence. The scope of the reaction was extended to substituted α-chloroacetophenones as well as various allyl alcohols.

Synthesis of polysubstituted tetrahydrofurans via Pd-catalyzed carboetherification reactions

Pd-catalyzed carboetherifications of 1-, 2-, or 3-substituted γ-hydroxy internal alkenes afford tetrahydrofuran products bearing three stereocenters in good yield with moderate to good stereoselectivity.

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.

Polar and steric substituent effects in 5-exo-trig cyclizations of 1-aryl-4-penten-1-oxyl radicals

A series of 1-aryl-substituted 4-penten-1-oxyl radicals 2 were generated from parent N-alkoxypyridinethiones 6. The intermediates 2 undergo 5-exo-trig cyclizations which are sensitive to polar and steric substituent effects. Thus, para groups in the aroma

Radical ion probes. 3. The importance of resonance vs strain energy in the design of SET probes based upon the cyclopropylcarbinyl → Homoallyl radical rearrangement

Aryl cyclopropyl ketones have frequently been used as probes for single-electron transfer in organic reactions. The implicit assumption in these studies is that upon one-electron reduction, the corresponding arylcyclopropylketyl anions will undergo ring opening in analogy to the cyclopropylcarbinyl free radical. Earlier work in our laboratory has shown that ring opening of arylcyclopropylketyl anions is kinetically and thermodynamically unfavorable when the only substituents on the cyclopropane ring are alkyl or H. This sluggishness is attributable to a loss of resonance energy upon ring opening which is not fully compensated by the relief of cyclopropane ring strain. Consequently, aryl cyclopropyl ketones are unsuitable probes for single-electron transfer. In this paper, we examine the effect of radical-stabilizing substituents (phenyl and vinyl) on the ring opening of arylcyclopropylketyl anions. We have studied the mechanism, kinetics, and products of decay of radical anions generated electrochemically from trans-1-benzoyl-2-phenylcyclopropane and 1-benzoyl-2-vinylcyclopropane. The radical anions generated from these precursors each undergo ring opening (k ≈ 106-7 s-1) which is estimated to be exothermic by ca. 2 kcal/mol.

AN EASY SYNTHESIS OF THE 2-PHENYLSULFONYL-SUBSTITUTED ALLYLIC BROMIDES AND ACETATES AND THEIR REACTIVITY TOWARDS NUCLEOPHILES

The reaction of phenyl vinyl sulfone with various aldehydes in the presence of a catalytic amount of DABCO furnishes in good yields the corresponding 2-phenylsulfonyl-substituted alcohols 5a-5e which can be easily converted into their acetates 2a-2b or into their allylically rearranged bromides 3a-3d.These reagents, in turn, react with nucleophiles (ketone enolates and cuprates) with an allylic rearrangement (SN2' mechanism) to give the functionalized unsaturated sulfones 6a-g and 7a-g.A palladium catalyzed reaction allows a stereo-controlled transformation of the sulfone 6b into the (Z,Z) skipped 1,4-diene 8.

Novel Synthetic Reactions Using Bis(2,2,2-trifluoroethoxy)triphenylphosphorane

Alkoxy-or (acyloxy)(2,2,2-trifluoroethoxy)triphenylphosphoranes which were prepared in situ by the ligand exchange of bis(2,2,2-trifluoroethoxy)triphenylphosphorane with alcohols or carboxylic acids were found to behave as potential alkylating or acylating reagents for the preparation of a variety of esters, amides, sulfides, and ketones.

Novel Synthetic Reactions Using Bis(2,2,2-trifluoroethoxy)diorganosulfuranes

Alkoxy- or acyloxysulfuranes prepared in situ by the ligand exchange of bis(2,2,2-trifluoroethoxy)diorganosulfuranes with alcohols or carboxylic acids were found to behave as a potential alkylating or acylating reagent for the preparation of unsymmetrical sulfides, ketones, and esters.