25109-98-2

Upstream product

• 100-42-5 styrene 
• 100-51-6 benzyl alcohol 
• 591-50-4 iodobenzene 
• 935-04-6 benzyl vinyl ether 
• 120-51-4 benzoic acid benzyl ester 
• 96-09-3 styrene oxide 
• 100-44-7 benzyl chloride 
• 51558-95-3 1-phenyl-2-(phenylselanyl)ethanol 
• 108-86-1 bromobenzene 
• 2195-64-4 phenyl nonaflate 
• 17763-67-6 Phenyl triflate 
• 1271-66-5 dimethyltitanocene 
• 98-86-2 acetophenone 
• 13735-81-4 1-styrenyloxytrimethylsilane 

Downstream Products

• 98-86-2 acetophenone 
• 65-85-0 benzoic acid 
• 1083-30-3 dihydrochalcone 
• 1603818-43-4 dimethyl (2S,4S)-2-(benzyloxy)-4-(5-nitro-1,3-dioxoisoindolin-2-yl)-2-phenylcyclopentane-1,1-dicarboxylate 
• 1603818-42-3 dimethyl (2S,4S)-2-(benzyloxy)-4-(5-methoxy-1,3-dioxoisoindolin-2-yl)-2-phenylcyclopentane-1,1-dicarboxylate 
• 1603818-44-5 dimethyl (2S,4S)-2-(benzyloxy)-4-(2,5-dioxopyrrolidin-1-yl)-2-phenylcyclopentane-1,1-dicarboxylate 
• 1603818-41-2 dimethyl (2S,4S)-2-(benzyloxy)-4-(1,3-dioxoisoindolin-2-yl)-2-phenylcyclopentane-1,1-dicarboxylate 

Relevant academic research and scientific papers

Selective Approaches to α- and β-Arylated Vinyl Ethers

We developed simple and efficient protocols for palladium-catalyzed regioselective α- and β-arylations of structurally diverse vinyl ethers. Both catalytic methods proceed under relatively mild reactions conditions applying to a broad substrate range including more complex compounds providing arylated glucal or isochromene. Lacking the common requirement of a large reagent excess, the transformations are highly economic and limiting the waste production. Results from computational studies (DFT) provided insight into the key factors determining the pronounced regioselectivities of the investigated reactions.

Deprotonation of Al2Me6 by Sterically Bulky NHCs: Scope, Rationale through DFT Studies, and Application in the Methylenation of Carbonyl Substrates

The sterically bulky NHCs 1,3-di-tert-butylimidazol-2-ylidene (ItBu), 1,3-di-tert-butylimidazolin-2-ylidene (StBu), and 1,3-di-tert-butyl-3,4,5,6-tetrahydripyrimidin-2-ylidene (C6-tBu) were found to readily react with excess Al2Me6 at room temperature to form salts 2, 3, and 4, respectively, consisting of the polynuclear Me3Al(μ3-CH2)(AlMe2)2(μ2-CH3)- anion associated with either the cation ItBu-H+, StBu-H+, or C6-tBu-H+. Such a reaction involving the deprotonation of an Al2Me6 moiety by a NHC does not proceed with less sterically hindered NHCs such as 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IDipp) and 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes), for which only the classical Lewis pair adducts (NHC)AlMe3 were isolated. In line with experimental and density functional theory (DFT) calculations data, such reactivity thus appears to be driven by steric frustration, resulting in the destabilization of the corresponding (NHC)AlMe3 adducts, then more prone to dissociate and hence allowing Al2Me6 activation/deprotonation. The DFT-estimated profile of the reaction of model adduct (ItBu)AlMe3 (I) with Al2Me6 agrees with a ready adduct dissociation at low energy cost, with a subsequent deprotonation of Al2Me6 by the NHC fragment to afford model salt II (isostructural to salt 2). Anion Me3Al(μ3-CH2)(AlMe2)2(μ2-CH3)- behaves as an efficient CH22- group transfer agent with the methylenation of aldehydes and ketones to afford the corresponding methylene organics in good conversions. Bonding analysis of the latter anion agrees with an enhanced nucleophilicity of the Al-CH2 moiety (compared to the Al-Me groups), in line with the observed reactivity. DFT calculations also allowed a detailed bonding description of the pentacoordinate methylene carbon in the anion Me3Al(μ3-CH2)(AlMe2)2(μ2-CH3)-.

Dynamic kinetic asymmetric [3 + 2] annulation reactions of aminocyclopropanes

We report the first example of a dynamic kinetic asymmetric [3 + 2] annulation reaction of aminocyclopropanes with both enol ethers and aldehydes. Using a Cu catalyst and a commercially available bisoxazoline ligand, cyclopentyl- and tetrahydrofurylamines were obtained in 69-99% yield and up to a 98:2 enantiomeric ratio using the same reaction conditions. The method gives access to important enantio-enriched nitrogen building blocks for the synthesis of bioactive compounds.

Petasis olefination in a continuous-flow microwave reactor: Exo-glycals from sugar lactones

An efficient Petasis olefination of sugar lactones under continuous-flow microwave conditions was developed. Their conversion into exo-glycals can be steered by adjusting the residence time and the concentration of the solution within the reactor. Applying a continuous-flow procedure, the reaction time can be shortened to less than three minutes, several hundred times shorter compared to values given in the literature for batch procedures. This setup is utilizable for a gram-scale synthesis of enol ethers and exo-glycals, in particular, such ones containing potentially (Lewis) acid sensitive acetalic protecting groups. Georg Thieme Verlag Stuttgart - New York.

A facile solid-phase synthesis of vinyl ethers using a selenium traceless linker

A simple, efficient and environmentally friendly procedure for the solid-phase synthesis of vinyl ethers in good yields and purities by reaction of polystyrene-supported 2-hydroxyalkyl selenide with primary or secondary organic halides and subsequent oxid

Convenient one-pot synthesis of vinyl ethers from phenyl 2-hydroxyalkyl selenides

Vinyl ethers were prepared with good yields in a one-pot, two-step transformation by O-alkylation reaction of phenyl 2-hydroxyalkyl selenides with primary or secondary organic halides followed by oxidation elimination with 30% hydrogen peroxide. Copyright

Chelation-Controlled, Palladium-Catalyzed Arylation of Vinyl Ethers

Chelation-controlled, palladium-catalyzed arylation of vinyl ethers with nitrogen-containing directing groups has been studied.Ethenyloxyalkylamines 1a-c and pyridines 2a-d, representing different carbon tethers were reacted with iodobenzene 4a and 1-iodonaphthalene 4b under phase-transfer conditions.The regioselectivity achieved is compared with the outcome from reactions with sterically similar vinyl ethers 3a-d.Arylations of the dimethylamine derivative 1a and the pyridine derivative 2a occurred at the terminal position of the olefins and were highly regioselective.A catalytic cycle for the regioselective, chelation-controlled vinylic substitution, involving a six-membered chelate ring, is proposed.

Comparative Substituent Effects of Tosyloxy, Benzyloxy, and Phosphoryloxy Substituents in Carbocation Formation. Acid-Catalized Hydration of Vinyl Tosylates, Benzoates, and 1,1-Ditosylates

Kinetc results for theacid-catalized hydration of alkenyl esters CH2=C(OX)R (X = Bz, Ts) and literature data for X = Ac and PO3Et2 are analyzed by the excess acidity method, and it is concluded that all the substrates react by the AdE2 mechanism of rate-limiting proton transfer to the double bond.Average substituent parameters ?p+ derived for the groups OBz, OAc, and OPO3Et2 of -0.18, -0.16, and -0.20, respectively, are similar and indicate these groups are modestly effective electron donors, while the average values of 0.08 for the OTs group indicates this to be a net electron withdrawing group.Hydrolysis of t-BuCH=C(OTs)2 requires much stronger acid; it has kH+/kD+ = 5.75 and a low slope of the rate versus acidity plot that is interpreted in terms of rate-limiting protonation of a substrate whose basic oxygens interact strongly with the acid solvent.

Carbonyl Methylenation Using a Titanium- Aluminum (Tebbe) Complex

The titanium-aluminum (Tebbe) complex is shown to be an effective methylenating agent for a variety of carbonyl groups.The reaction is unique in that the carbonyl groups of carboxylic acid derivatives are readily methylenated.Thus vinyl enol ethers are prepared from esters and enamines are formed from amides.The complex provides a method for methylenating hindered or base sensitive ketones that is advantageous to the Wittig reagent.Selective methylenation of dicarbonyl compounds is also accomplished.