329796-90-9

Basic information

• Product Name: (R)-4-(1-hydroxy-but-3-enyl)-benzoic acid methyl ester
• Synonyms: (R)-4-(1-hydroxy-but-3-enyl)-benzoic acid methyl ester
• CAS NO: 329796-90-9
• Molecular Weight: 206.241
• Mol File: 329796-90-9.mol

Chemical Properties

• CAS DataBase Reference: (R)-4-(1-hydroxy-but-3-enyl)-benzoic acid methyl ester(CAS DataBase Reference)
• NIST Chemistry Reference: (R)-4-(1-hydroxy-but-3-enyl)-benzoic acid methyl ester(329796-90-9)
• EPA Substance Registry System: (R)-4-(1-hydroxy-but-3-enyl)-benzoic acid methyl ester(329796-90-9)

Safety Data

• Hazardous Substances Data: 329796-90-9(Hazardous Substances Data)

Upstream product

• 1571-08-0 methyl 4-formylbenzoate 
• 1730-25-2 allylmagnesium bromide 
• 106-95-6 allyl bromide 
• 124-41-4 sodium methylate 
• 85116-38-7 (+)-diisopinocampheylallylborane 
• 619-66-9 4-Carboxybenzaldehyde 
• 124821-92-7 d-B-allylbis(2-isocaranyl)borane 
• 99493-25-1 diisopropyl (R,R)-2-allyl-1,3,2-dioxaborolane-4,5-dicarboxylate 
• 6908-41-4 4-(methoxycarbonyl)benzyl alcohol 
• 591-87-7 Allyl acetate 
• 72824-04-5 2-Allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 369651-27-4 (1S,2S,5R)-1-allyl-2-isopropyl-5-methylcyclohexanol 

Downstream Products

• 329796-98-7 4-((R)-1-Hydroxy-but-3-enyl)-benzoic acid 

Relevant articles and documents

Bi(cyclopentyl)diol-Derived Boronates in Highly Enantioselective Chiral Phosphoric Acid-Catalyzed Allylation, Propargylation, and Crotylation of Aldehydes

In this study, we disclose the catalytic addition of bi(cyclopentyl)diol-derived boronates to aldehydes promoted by chiral phosphoric acids, allowing for the formation of enantioenriched homoallylic, propargylic, and crotylic alcohols (up to >99% enantiom

Heteropoly Acid Supported on Silica Gel as Catalyst for the Asymmetric Transfer Allylation of Aromatic Aldehydes under Solvent-Free Conditions

A new convenient method for the asymmetric transfer allylation of aromatic aldehydes was developed. The reaction gave the best results using a chiral allyl donor molecule derived from (-)-menthone in the presence of heteropoly acids supported on silica gel under solvent-free conditions, and the desired homoallylic alcohol derivatives were obtained in good yields with good to high enantioselectivity.

Br?nsted acid-catalyzed asymmetric allylation and propargylation of aldehydes

A method synthesizing homoallylic or homopropargylic alcohols was developed to react aldehydes with allyl boronates, such as allylboronic acid pinacol ester, or allenylborates in the presence of a catalytic amount of a chiral binaphthyl-derived chiral pho

Asymmetric allylboration of aldehydes with pinacol allylboronates catalyzed by 1,1′-spirobiindane-7,7′-diol (SPINOL) based phosphoric acids

The asymmetric allylboration of aldehydes with pinacolallylboronates catalyzed by 1,1′-spirobiindane-7,7′-diol (SPINOL) based phosphoric acids is described. 6,6′-Bis(2,4,6-triisopropylphenyl)SPINOL-based phosphoric acid was found to be a general, highly e

Chiral bronsted acid-catalyzed allylboration of aldehydes

The catalytic enantioselective allylation of aldehydes is a long-standing problem of considerable interest to the chemical community. We disclose a new high-yielding and highly enantioselective chiral Bronsted acid-catalyzed allylboration of aldehydes. Th

Indium-mediated asymmetric Barbier-type allylations: Additions to aldehydes and ketones and mechanistic investigation of the organoindium reagents

(Chemical Equation Presented) We report a simple, efficient, and general method for the indium-mediated enantioselective allylation of aromatic and aliphatic aldehydes and ketones under Barbier-type conditions in a one-pot synthesis affording the corresponding chiral alcohol products in very good yield (up to 99%) and enantiomeric excess (up to 93%). Our method is able to tolerate various functional groups, such as esters, nitriles, and phenols. Additionally, more substituted allyl bromides, such as crotyl and cinnamyl bromide, can be used providing moderate enantioselectivity (72% and 56%, respectively) and excellent diastereoselectivity when employing cinnamyl bromide (95/5 anti/syn). However, the distereoselectivity when using crotyl bromide was poor and other functionalized allyl bromides under our method afforded low enantioselectivities for the alcohol products. In these types of indium-mediated additions, solvent plays a major role in determining the nature of the organoindium intermediate and we observed the susceptibility of some allylindium intermediates to hydrolysis in protic solvents. Under our reaction conditions using a polar aprotic solvent, we suggest that an allylindium(III) species is the active allylating intermediate. In addition, we have observed the presence of a shiny, indium(0) nugget throughout the reaction, irrespective of the stoichiometry, indicating disproportionation of indium halide byproduct formed during the reaction.

Enantioselective iridium-catalyzed carbonyl allylation from the alcohol or aldehyde oxidation level via transfer hydrogenative coupling of allyl acetate: Departure from chirally modified allyl metal reagents in carbonyl addition

Under the conditions of transfer hydrogenation employing an iridium catalyst generated in situ from [Ir(COd)Cl]2, chiral phosphine ligand (R)-BINAP or (R)-Cl,MeO-BIPHEP, and m-nitrobenzoic acid, allyl acetate couples to allylic alcohols 1a-c, aliphatic alcohols 1d-1, and benzylic alcohols 1m-u to furnish products of carbonyl allylation 3a-u with exceptional levels of asymmetric induction. The very same set of optically enriched carbonyl allylation products 3a-u are accessible from enals 2a-c, aliphatic aldehydes 2d-1, and aryl aldehydes 2m-u, using iridium catalysts ligated by (-)-TMBTP or (R)-Cl,MeO-BIPHEP under identical conditions, but employing isopropanol as a hydrogen donor. A catalytically active cyclometallated complex V, which arises upon ortho-C-H insertion of iridium onto m-nitrobenzoic acid, was characterized by single-crystal X-ray diffraction. The results of isotopic labeling are consistent with intervention of symmetric iridium π-allyl intermediates or rapid interconversion of σ-allyl haptomers through the agency of a symmetric π-allyl. Competition experiments demonstrate rapid and reversible hydrogenation-dehydrogenation of the carbonyl partner in advance of C-C coupling. However, the coupling products, which are homoallylic alcohols, experience very little erosion of optical purity by way of redox equilibration under the coupling conditions, although isopropanol, a secondary alcohol, may serve as terminal reductant. A plausible catalytic mechanism accounting for these observations is proposed, along with a stereochemical model that accounts for the observed sense of absolute stereoinduction. This protocol for asymmetric carbonyl allylation transcends the barriers imposed by oxidation level and the use of preformed allyl metal reagents.

Enantioselective iridium-catalyzed carbonyl allylation from the alcohol or aldehyde oxidation level using allyl acetate as an allyl metal surrogate

Protocols for highly enantioselective carbonyl allylation from the alcohol or aldehyde oxidation level are described based upon transfer hydrogenative C-C coupling. Exposure of allyl acetate to benzylic alcohols 1a-i in the presence of an iridium catalyst derived from [IrCl(cod)]2 and (R)-BINAP delivers products of C-allylation 2a-i. Employing isopropanol as terminal reductant, exposure of allyl acetate to aryl aldehydes 3a-i in the presence of an iridium catalyst derived from [IrCl(cod)]2 and (-)-TMBTP delivers identical products of C-allylation 2a-i. In all cases examined, exception levels of enantioselectivity are observed. Thus, enantioselective carbonyl allylation is achieved from the alcohol or aldehyde oxidation level in the absence of any preformed allylmetal reagents. These studies define a departure from preformed organometallic reagents in carbonyl additions that transcend the boundaries of oxidation level. Copyright

Competitive cationic pathways and the asymmetric synthesis of aryl-substituted cyclopropanes

Equation presented 1,2-Disubstituted cyclopropanes were synthesized in a nonracemic fashion via activation of the corresponding homoallylic alcohols in excellent yields. A series of substituted phenyl rings showed higher enantiospecificity for the cyclization as the electron-withdrawing ability of the group increased. The results offer strong support for the existence of competing cation mechanisms.

Stereoselective allylation of aldehydes on solid support and its application in biology-oriented synthesis (BIOS)

A systematic study on the asymmetric allylation of aldehydes on solid support is reported. Different kinds of chiral allylboron reagents with complementary direction of stereoinduction were applied successfully in this reagent-controlled transformation. T