163667-14-9

Upstream product

• 99808-99-8 (R,S)-α-[(tert-butyldimethylsilyl)oxy]-α-(phenyl)acetonitrile 
• 135348-18-4 (tert-Butyl-dimethyl-silanyloxy)-phenyl-acetic acid ethyl ester 
• 100-52-7 benzaldehyde 
• 121618-58-4 trans-tert-butyldimethyl(((2S,3S)-3-phenyloxiran-2-yl)methoxy)silane 
• 611-71-2 MANDELIC ACID 
• 56522-24-8 tert-butyldimethylsilyl cyanide 
• 18162-48-6 tert-butyldimethylsilyl chloride 
• 4358-87-6 (RS)-methyl mandelate 
• 4393-06-0 1-Phenyl-2-propen-1-ol 
• 774-40-3 hydroxy-phenyl-acetic acid ethyl ester 
• 5849-19-4 <1,3>dithian-2-yl-phenyl-methanol 
• 568597-19-3 tert-butyl-([1,3]dithian-2-yl-phenyl-methoxy)-dimethyl-silane 
• 73795-12-7 1-phenylprop-2-en-1-yl tert-butyldimethylsilyl ether 
• 148204-86-8 (tert-butyldimethylsilanyloxy)phenylacetic acid methyl ester 

Downstream Products

• 1040285-11-7 (E)-4-(tert-butyldimethylsilanyloxy)-4-phenylbut-2-enoic acid methyl ester 
• 146405-41-6 [2-(tert-butyl-dimethyl-silanyloxy)-2-phenyl-ethylidene]-trimethylsilanyl-amine 
• 103548-04-5 2-(tert-butyldimethylsilanyloxy)-1-phenylethan-1-one 
• 1021306-03-5 C₂₂H₂₈O₂Si 
• 1003279-96-6 tert-butyl (RS,E)-4-(tert-butyldimethylsilyloxy)-4-phenylbut-2-enoate 
• 709631-31-2 (Z)-4-(tert-butyldimethylsilanyloxy)-4-phenylbut-2-enoic acid methyl ester 

Relevant academic research and scientific papers

The influence of α-coordinating groups of aldehydes on E/Z-selectivity and the use of quaternary ammonium counter ions for enhanced E-selectivity in the Julia–Kocienski reaction

Modified reaction conditions for improved E-selectivity of olefins in the Julia–Kocienski reaction of aldehydes having α-coordinating substituents are demonstrated. The chelating groups in aldehydes are expected to stabilize the syn-transition state with metal ions, whereas the weakly coordinating quaternary ammonium ions are devoid of all possible chelating interactions to enhance E-selectivity. A systematic investigation is presented to study the size of the neighbouring protecting groups of aldehydes and their chelation effect on E/Z-selectivity in the Julia–Kocienski reaction.

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 Highly Substituted Furans by a Cascade of Formal anti-Carbopalladation/Hydroxylation and Elimination

Highly substituted furans are generated by a cascade of formal anti-carbopalladation, attack of a nucleophilic hydroxy group, and aromatization by elimination of the emerging dihydrofuran derivative. Mono-, di-, and trisubstituted furans were obtained in good to excellent yields. When we attempted to access tetrasubstituted furan derivatives, an additional rearrangement was observed that resulted in the formation of chromenes. Follow-up chemistry shows the utility of TMS as a protecting group for the alkyne moiety.

Enantioselective aerobic oxidation of α-hydroxy-ketones catalyzed by oxidovanadium(V) methoxides bearing chiral, N-salicylidene- tert -butylglycinates

Chiral oxidovanadium(V) methoxides prepared from 3,5-disubstituted-N- salicylidene-l-tert-butylglycines and vanadyl sulfate in air-saturated MeOH serve as highly enantioselective catalysts for asymmetric aerobic oxidations and kinetic resolution of alkyl, aryl, and heteroaryl α-hydroxy-ketones with differed α-substituents at ambient temperature in toluene or TBME (tert-butyl methyl ether). The best scenarios involve the use of complexes which bear the tridendate templates derived from 3,5-diphenyl- or 3-o-biphenyl-5-nitro-salicyaldehyde. The kinetic resolution selectivities of the aerobic oxidation process are in the range of 12 to >1000 based on the selectivity factors (krel).

β-fluoroamphetamines via the stereoselective synthesis of benzylic fluorides

A range of substituted aryl epoxides undergo efficient ring-opening hydrofluorination upon treatment with 0.33 equiv of BF3-OEt 2 in CH2Cl2 at -20 -°C to give the corresponding syn-fluorohydrins, consistent with a mechanism involving a stereoselective SN1-type epoxide ring-opening process. The benzylic fluoride products of these reactions are valuable templates for further elaboration, as demonstrated by the preparation of a range of aryl-substituted β-fluoroamphetamines.

A convenient and versatile method for the preparation of α-hydroxymethyl ketone derivatives from the corresponding allyl silyl ethers or allyl carboxylates

The ozonolysis of 1-substituted allyl silyl ethers or 1-substituted allyl carboxylates followed by treatment with bases gave the corresponding α-silyloxymethyl- or α-acyloxymethyl-ketones in good yields. It is proposed to proceed via the corresponding α-silyloxy- or α-acyloxyaldehydes intermediates followed by 1,4-group migration. The results of theoretical calculations are applicable to explain the experimental results.

Ether-directed diastereoselectivity in catalysed Overman rearrangement: comparative studies of metal catalysts

Ether-directed diastereoselectivity in Overman rearrangement of δ-methoxy and δ-TBDMSO substituted allylic trichloroacetimidates has been explored using PtCl2, PtCl4, AuCl and AuCl3 catalysts in comparison with commonly us

Synthesis of 3-fluorofuran-2(5H)-ones based on Z/E photoisomerisation and cyclisation of 2-fluoro-4-hydroxybut-2-enoates

Mixtures of some (E)- and (Z)-2-fluoroalk-2-enoates prepared from the corresponding 2-hydroxycarbonyl compounds and ethyl 2-(diethoxyphosphoryl)-2- fluoroacetate have been transformed in high conversions into the target 3-fluorofuran-2(5H)-ones by an effi

Tishchenko reactions of aldehydes promoted by diisobutylaluminum hydride and its application to the macrocyclic lactone formation

Aliphatic aldehydes react with catalytic amount of Dibal-H in n-pentane to give the corresponding Tishchenko products in good to excellent yields. On contrary, α-silyloxy aldehydes give α-silyloxy ketones via Oppenauer oxidation under similar condition. Tishchenko reaction of ω-alkene aldehydes followed by RCM and hydrogenation affords a convenient method to prepare the 11-37 membered macrocyclic lactones.

Synthetic applications of the amine-base treatment in the ozonolysis of substituted-allyl silyl ethers or -allyl esters via a novel ene-diol type rearrangement

The ozonolysis of substituted-allyl silyl ethers or -allyl esters followed by treatment with bases gave the corresponding α-silyloxy ketones or α-acyloxy ketones in good yields. The reaction is proposed to proceed via a novel ene-diol rearrangement of the corresponding α-silyloxy aldehydes or α-acyloxy aldehydes intermediates.