80698-15-3

Basic information

• Product Name: α-methyl-δ-valerolactone
• Synonyms: α-methyl-δ-valerolactone
• CAS NO: 80698-15-3
• Molecular Weight: 114.144
• Mol File: 80698-15-3.mol

Chemical Properties

• CAS DataBase Reference: α-methyl-δ-valerolactone(CAS DataBase Reference)
• NIST Chemistry Reference: α-methyl-δ-valerolactone(80698-15-3)
• EPA Substance Registry System: α-methyl-δ-valerolactone(80698-15-3)

Safety Data

• Hazardous Substances Data: 80698-15-3(Hazardous Substances Data)

Upstream product

• 542-28-9 3,4,5,6-tetrahydro-2H-pyran-2-one 
• 74-88-4 methyl iodide 
• 1120-72-5 2-Methylcyclopentanone 
• 821-09-0 n-Pent-4-enyl alcohol 
• 201230-82-2 carbon monoxide 
• 64180-78-5 4-bromopent-4-en-1-ol 
• 26093-63-0 3-methyltetrahydropyran 
• 31468-33-4 2-methylglutaric anhydride 
• 108-18-9 diisopropylamine 
• 68258-41-3 3-methylpyran-2-ol 
• 73758-10-8 4-((4S,5S)-4-Methoxymethyl-5-phenyl-4,5-dihydro-oxazol-2-yl)-hexan-1-ol 
• 91606-67-6 pent-4-enyl chloroformate 
• 79964-12-8 2-methyl-acrylic acid but-3-enyl ester 
• 72649-02-6 5,6-dihydro-3-methyl-2H-pyran-2-one 

Downstream Products

• 107326-72-7 ((2E,7E)-(R)-4-Methyl-deca-2,7,9-trienyloxymethyl)-benzene 
• 107326-73-8 2-[(1R,2R,5R)-2-Methyl-5-((Z)-propenyl)-cyclopentylmethyl]-[1,3]dioxolane 
• 107326-73-8 2-[(1S,2R,5S)-2-Methyl-5-((Z)-propenyl)-cyclopentylmethyl]-[1,3]dioxolane 
• 808766-14-5 (R)-4-benzyl-3-((2R,3S,4S,5R,8S)-3,5-dihydroxy-2,4,8-trimethylundec-9-ynoyl)oxazolidin-2-one 
• 808765-97-1 (2R,4S,5R,8S)-1-((R)-4-benzyl-2-oxooxazolidin-3-yl)-5-hydroxy-2,4,8-trimethylundec-9-yne-1,3-dione 
• 4457-71-0 3-methylpentane-1,5-diol 

Relevant articles and documents

Acid-Catalyzed Hydrolysis of a (γ-Hydroxyalkyl)ketene Dithioacetal. A Cyclic Intermediate and Product Distribution

2-(Hydroxyalkylidene)-1,3-dithiane 1a undergoes acid-catalyzed hydrolysis.Disappearance of 1a is faster than formation of the products thio ester 5a and lactone 5a'.The product distribution changes with pH in a similar way to that of hydrolysis of the cyclic intermediate 3a.Hydrolysis of 1a must proceed mostly through 3a, accompanying its accumulation.In comparison with the reference substrate 1b, anchimeric assistance by the internal hydroxyl group was not observed in wholly aqueous solution, but it becomes apparent in aqueous acetonitrile solutions at high organic concentration.Neighboring hydroxyl participation is considered to occur by internal solvation, and the carbocation 2a can exist as a discrete intermediate of the hydrolysis.

Enantioselective Construction of Quaternary Carbon Stereocenter via Palladium-Catalyzed Asymmetric Allylic Alkylation of Lactones

An efficient and practical method for the synthesis of α,α-disubstituted six-membered lactones was developed. Enantioselective construction of quaternary carbon centers by utilizing Pd-catalyzed asymmetric allylic alkylation proved its feasibility.

LYMPH DIRECTING PRODRUGS

H:\dar\Interwoven\NRPortbl\DCC\DAR\8230712_1.doc-12/08/2015 Abstract The present invention relates to compounds and their uses, in particular, compounds in the form of prodrugs that promote transport of a pharmaceutical agent to the lymphatic system and subsequently enhance release of the parent drug.

Biocatalytic Characterization of Human FMO5: Unearthing Baeyer-Villiger Reactions in Humans

Flavin-containing mono-oxygenases are known as potent drug-metabolizing enzymes, providing complementary functions to the well-investigated cytochrome P450 mono-oxygenases. While human FMO isoforms are typically involved in the oxidation of soft nucleophiles, the biocatalytic activity of human FMO5 (along its physiological role) has long remained unexplored. In this study, we demonstrate the atypical in vitro activity of human FMO5 as a Baeyer-Villiger mono-oxygenase on a broad range of substrates, revealing the first example to date of a human protein catalyzing such reactions. The isolated and purified protein was active on diverse carbonyl compounds, whereas soft nucleophiles were mostly non- or poorly reactive. The absence of the typical characteristic sequence motifs sets human FMO5 apart from all characterized Baeyer-Villiger mono-oxygenases so far. These findings open new perspectives in human oxidative metabolism.

Aldol Additions of Titanium and Boron Enolates of Achiral and Chiral δ-Lactones to Achiral Model Aldehydes: Simple and Induced Diastereoselectivities

We studied the steric course of aldol additions of CpTiCl2 (novel) or Bu2B enolates of the unsubstituted δ-lactone and of the four monomethylated δ-lactones to isobutyraldehyde, crotonaldehyde, and para-bromobenzaldehyde. The titanium enolates reacted syn-selectively with >95:5 ds in most cases. The boron enolates reacted anti-selectively without exception (ds = 98:2 to 92:8). These selectivities paired with a preferred trans-orientation of the α-hydroxyalkyl substituents relative to the lactone's β- or γ-methyl group and with a preferred cis-orientation relative to the lactone's δ-methyl group. Our preparation of γ-methyl-δ-lactone (20) features a tandem glycol cleavage/lactol → lactone conversion with cat. TEMPO/stoichiom. PhI(OAc)2, which we believe is novel. Aldol additions of CpTiCl2 and Bu2B enolates of δ-lactone and its monomethyl derivatives to model aldehydes were studied. The CpTiCl2 enolates reacted syn-selectively (ds >95:5), the Bu2B enolates anti-selectively (ds up to 98:2). The α-hydroxyalkyl groups were oriented trans relative to the lactone's β- or γ-methyl group but cis relative to the lactone's δ-methyl group.

Functional divergence between closely related Baeyer-Villiger monooxygenases from Aspergillus flavus

Baeyer-Villiger monooxygenases (BVMOs) catalyse the chemo-, regio- and enantioselective oxidation of ketones to esters and lactones. To date, most of the cloned BVMOs available are derived from bacteria, although Baeyer-Villiger oxidations using fungi have frequently been demonstrated. Here we report the cloning and characterization of four BVMOs from the fungus Aspergillus flavus NRRL3357. Phylogenetic analysis shows these four BVMOs to cluster in a distinct group apart from other well-characterized BVMOs including cyclohexanone, phenylacetone and 4-hydroxyacetophenone monooxygenase. Building on the Grogan classification/clustering of BVMOs, we have designated this new group of BVMOs, Group VI. Group VI BVMOs show an early divergence from the cyclopentanone monooxygenase (CPMO) type BVMOs (Group I). Substrate profiling using cyclic, bicyclic, aliphatic and aryl ketones show a clear divergence in function and specificity not only between this new group of BVMOs and the CPMO-type BVMOs, but also between the four A. flavus BVMO paralogues despite their high sequence similarity. This study not only contributes to the growing number of available BVMOs, but also addresses the current classification of Type I BVMOs, and the usefulness of phylogenetic clustering and prediction of function and selectivity when genome-mining is used to search for new biocatalysts.

Catalytic oxidation of cyclic ethers to lactones over various titanosilicates

Various crystalline microporous metallosilicates have been used in the liquid phase catalytic oxidation of different cyclic ethers into their corresponding lactones in the presence of dilute aqueous H2O 2 as oxidant. Among the various metallosilicates studied for the oxidation of tetrahydrofuran to γ-butyrolactone, titanosilicates exhibited the best activity than the other metallosilicates such as chromium silicalite-1 (CrS-1), chromium silicalite-2 (CrS-2) and vanadium silicalite-1 (VS-1). The intrinsic activity of TS-1 was found to be marginally higher than the other titanosilicates. Cyclic ethers undergo αC-H oxidation to give the corresponding lactones; whereas open-chain ether produce carboxylic acids by initial αC-H bond oxidation to give ester as an intermediate product, which further undergoes cleavage of -O- linkage to give the final carboxylic acids. The conversion of substituted tetrahydrofuran is decreased with number of -CH3 groups at α- and/or β-position. The lactone formation is hindered when both the α-positions are substituted with methyl substituents. Mechanistically, titanium hydroperoxo complex formed in the titanosilicate/H2O2/H2O system is believed to oxidize the αC-H bond of ethers producing the respective α-hydroxylated product, which undergoes further oxidation to give the lactones (for cyclic ethers) or carboxylic acids (for open-chain ethers).

Exploration of the interrupted Fischer indolization reaction

A convergent method to access the fused indoline ring system present in a multitude of bioactive molecules has been developed. The strategy involves the condensation of hydrazines with latent aldehydes to ultimately deliver indoline-containing products by way of an interrupted Fischer indolization sequence. The method is convergent, mild, operationally simple, broad in scope, and can be used to access enantioenriched products. In addition, our approach is amenable to the synthesis of furoindoline and pyrrolidinoindoline natural products as demonstrated by the concise formal total syntheses of physovenine and debromoflustramine B. The strategy will likely enable the synthesis of more complex targets such as the communesin alkaloids.

Remote control of regio- and diastereoselectivity in the hydroformylation of bishomoallylic alcohols with catalytic amounts of a reversibly bound directing group

(Figure Presented) Remote and reversible! Phosphinites serve as reversibly bound directing groups for the remote control of the regio- and diastereoselective hydroformylation of bishomoallylic alcohols (see scheme; r.r: regioisomer ratio). The distance between the double bond and the functional hydroxy group to which the directing group is reversibly bound is the longest ever reported.

An interrupted fischer indolization approach toward fused indoline-containing natural products

An efficient method to access the fused indoline ring system present in a multitude of bioactive molecules has been developed. The strategy involves the condensation of hydrazines with latent aldehydes to ultimately deliver indoline-containing products by way of an interrupted Fischer indolization sequence. Our studies show that the approach will likely be amenable to the synthesis of complex targets, such as the communesin natural products.