Derivatization Method Research Articles

Rapid chiral discrimination of oncometabolite dl-2-hydroxyglutaric acid using derivatization and field asymmetric waveform ion mobility spectrometry/mass spectrometry.

2-Hydroxyglutaric acid is a chiral metabolite whose enantiomers specifically accumulate in different diseases. An enantiomeric excess of the d-form in biological specimens reflects the existence of various pathogenic mutations in cancer patients, however, conventional methods using gas or liquid chromatography and capillary electrophoresis had not been used for large clinical studies because they require multiple analytical instruments and a long run time to separate the enantiomers. Here, we present a rapid separation method for dl-2-hydroxyglutaric acid using a chiral derivatizing reagent and field asymmetric waveform ion mobility spectrometry/mass spectrometry, which requires a single analytical instrument and <1 s for the separation. We compared three derivatization methods and found that a method using (S)-1-(4,6-dimethoxy-1,3,5-triazin-2-yl)pyrrolidin-3-amine enables the separation. In addition, we were able to detect dl-2-hydroxyglutaric acid in standard solution at lower concentrations than that previously reported for the serum. These results show the potential of the method to be used in clinical analysis.

Simultaneous Determination of Nine Perfluoroalkyl Carboxylic Acids in Chinese Wolfberry and Soybean by Gas Chromatography–Mass Spectrometry with a Novel Derivatization Method

Simultaneous Determination of Nine Perfluoroalkyl Carboxylic Acids in Chinese Wolfberry and Soybean by Gas Chromatography–Mass Spectrometry with a Novel Derivatization Method

Quantitative GC determination of sodium triacetoxyborohydride (STAB)

Sodium triacetoxyborohydride (STAB) is a mild, selective, and frequently used reducing agent for reductive amination transformations. STAB has been reported to undergo degradation when exposed to air, often requiring additional sub-stoichiometric reagent charges to drive reactions to completion. We report the development and qualification of a rapid, quantitative GC derivatization method using 3,4-dihydroisoquinoline to enable accurate hydride assay determination of STAB. Assay data generated from this method has been directly compared to a recently published HPLC method using bromosalicaldehyde as the derivatization reagent. The degradation kinetics of STAB have also been further investigated by Raman spectroscopy to demonstrate how exposure of STAB to air can negatively impact the reagent’s performance.

Trocylation of 3-quinuclidinol, a key marker for the chemical warfare agent 3-quinuclidinyl benzilate, for its enhanced detection at low levels in complex soil matrices by electron ionization gas chromatography-mass spectrometry.

Detection of 3-quinuclidinol (3Q), a marker for the chemical warfare agent 3-quinuclidinyl benzilate, is very difficult by gas chromatography-mass spectrometry (GC/MS), providing low, broad signals even when analyzed in isolated form. Therefore, a method that can convert 3Q into a substrate with enhanced detectability by GC/MS would be an important tool for its analysis. 2,2,2-Trichloroethoxycarbonyl chloride (TrocCl) was used in the derivatization of 3Q in three different soils of varying composition and total organic content (Virginia type A soil, Nebraska EPA standard soil and Ottawa sand) when present at a 10μg g-1 concentration in each. A direct derivatization protocol and one involving the pre-extraction of the analyte were evaluated for their individual efficiencies and subsequent analysis using electron ionization GC/MS. The practical derivatization of 3Q, when present at low levels (10μg g-1 ) in three different soil matrices, was found to be rapid (1h) and to take place smoothly at ambient temperature (and as low as 4°C). The method detection limit was determined to be 30 ng mL-1 for the Virginia type A soil, 49 ng mL-1 for the Nebraska EPA standard soil and 72 ng mL-1 for the Ottawa sand sample. An expedient and practical derivatization method for 3Q, a chemical warfare degradation product difficult to detect by GC/MS, has been realized using trichloroethyl chloroformate. The reaction provides 3Q-Troc, a derivative with better detectability than 3Q by electron ionization GC/MS such as peak sharpness and a unique mass spectrum for its unambiguous identification.

Development of an Efficient and Sensitive Chemical Derivatization-Based LC-MS/MS Method for Quantifying Gut Microbiota-Derived Metabolites in Human Plasma and Its Application in Studying Cardiovascular Disease.

Recently, the gut microbiota has been found to be associated with many diseases, such as inflammatory bowel disease, depression, Parkinson's disease, cancer, metabolic syndrome, and cardiovascular disease (CVD). Among various gut microbiota-derived metabolites (GMs), short-chain fatty acids (SCFAs), bile acids (BAs), and tryptophan (TRP) metabolites are the most frequently discussed metabolites. LC-MS/MS shows advantages in quantifying the levels of metabolites with good sensitivity and selectivity; however, the poor ionization efficiency and polar characteristics of SCFAs make their analysis challenging, especially when analyzing plasma samples with low SCFA concentrations. Moreover, without characteristic fragment ions for unconjugated BAs and different detection ion modes for TRP metabolites and BAs, GM analysis is complex and time-consuming. To overcome these problems, we developed a derivatization method combined with LC-MS/MS to enhance the sensitivity and LC retention of GMs. Through derivatization with 3-nitrophenylhydrazine (3-NPH), 7 SCFAs, 9 bile acids, and 6 tryptophan metabolites can be simultaneously analyzed via separation within 14 min on a reversed-phase C18 column. For accurate quantification, 13C6-3NPH-labeled standards were used as one-to-one internal standards. This derivatization approach was optimized and then validated. We further applied this method to investigate the targeted GM profile in patients with CVD. The results showed a significant reduction in plasma butyrate levels in CVD patients compared with healthy controls, suggesting its potentially protective role in CVD. In summary, this work provides a sensitive and effective LC-MS/MS method for simultaneously quantifying gut microbiota-related metabolites in human plasma, which could benefit various future gut microbiota-related studies.

GC-MS Studies on Derivatization of Creatinine and Creatine by BSTFA and Their Measurement in Human Urine.

In consideration of its relatively constant urinary excretion rate, creatinine (2-amino-1-methyl-5H-imidazol-4-one, MW 113.1) in urine is a useful endogenous biochemical parameter to correct the urinary excretion rate of numerous endogenous and exogenous substances. Reliable measurement of creatinine by gas chromatography (GC)-based methods requires derivatization of its amine and keto groups. Creatinine exists in equilibrium with its open form creatine (methylguanidoacetic acid, MW 131.1), which has a guanidine and a carboxylic group. Trimethylsilylation and trifluoroacetylation of creatinine and creatine are the oldest reported derivatization methods for their GC-mass spectrometry (MS) analysis in human serum using flame- or electron-ionization. We performed GC-MS studies on the derivatization of creatinine (d0-creatinine), [methylo-2H3]creatinine (d3-creatinine, internal standard) and creatine (d0-creatine) with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) using standard derivatization conditions (60 min, 60 °C), yet in the absence of any base. Reaction products were characterized both in the negative-ion chemical ionization (NICI) and in the positive-ion chemical ionization (PICI) mode. Creatinine and creatine reacted with BSTFA to form several derivatives. Their early eluting N,N,O-tris(trimethylsilyl) derivatives (8.9 min) were found to be useful for the precise and accurate measurement of the sum of creatinine and creatine in human urine (10 µL, up to 20 mM) by selected-ion monitoring (SIM) of m/z 271 (d0-creatinine/d0-creatine) and m/z 274 (d3-creatinine) in the NICI mode. In the PICI mode, SIM of m/z 256, m/z 259, m/z 272 and m/z 275 was performed. BSTFA derivatization of d0-creatine from a freshly prepared solution in distilled water resulted in formation of two lMate-eluting derivatives (14.08 min, 14.72 min), presumably creatinyl-creatinine, with the creatininyl residue existing in its enol form (14.08 min) and keto form (14.72 min). Our results suggest that BSTFA derivatization does not allow specific analysis of creatine and creatinine by GC-MS. Preliminary analyses suggest that pentafluoropropionic anhydride (PFPA) is also not useful for the measurement of creatinine in the presence of creatine. Both BSTFA and PFPA facilitate the conversion of creatine to creatinine. Specific measurement of creatinine in urine is possible by using pentafluorobenzyl bromide in aqueous acetone.

Sample preparation strategy for the detection of steroid-like compounds using MALDI mass spectrometry imaging: pulmonary distribution of budesonide as a case study

Corticosteroids as budesonide can be effective in reducing topic inflammation processes in different organs. Therapeutic use of budesonide in respiratory diseases, like asthma, chronic obstructive pulmonary disease, and allergic rhinitis is well known. However, the pulmonary distribution of budesonide is not well understood, mainly due to the difficulties in tracing the molecule in lung samples without the addition of a label. In this paper, we present a matrix-assisted laser desorption/ionization mass spectrometry imaging protocol that can be used to visualize the pulmonary distribution of budesonide administered to a surfactant-depleted adult rabbit. Considering that budesonide is not easily ionized by MALDI, we developed an on-tissue derivatization method with Girard’s reagent P followed by ferulic acid deposition as MALDI matrix. Interestingly, this sample preparation protocol results as a very effective strategy to raise the sensitivity towards not only budesonide but also other corticosteroids, allowing us to track its distribution and quantify the drug inside lung samples.Graphical abstract

Derivatization strategy for semi-quantitative analysis of medium- and long-chain fatty acids using multiple reaction monitoring

Medium- and long-chain fatty acids (MLFAs) are essential energy sources in cells and possess vital biological functions. Characteristics of MLFAs in biosamples contributes to the understanding of biological process and finding potential biomarkers for relevant diseases. However, there are obstacles of the MLFAs determination due to their poor ionization efficiency in mass spectrometry and structural similarity of the MLFAs. Herein, a derivatization strategy was applied by labeling with d0-N, N-dimethyl-6,7-dihydro-5H-pyrrolo [3,4-d] pyrimidine-2-amine (d0-DHPP) and detecting with ultra-high performance liquid chromatography combined with tandem mass spectrometry (UHPLC-MS/MS) in multiple reaction monitoring (MRM) mode. The parallel isotope labeled internal standards were generated by tagging d6-DHPP to MLFAs. The simple and rapid derivatization procedure and mild reaction conditions greatly reduced the potential of MLFA degradation during the processing procedure. With the methodology, the chromatographic performance was greatly improved, and the mass spectrum response was enhanced up to 1, 600 folds. Finally, the developed derivatization method was applied to serum samples to analyze the alteration of MLFAs induced by 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) exposure in breast cancer nude mice. The semi-quantitative results demonstrated that the BDE-47 exposure significantly influenced the MLFA metabolism in mice.

Characteristics of Electrospray-Ionization Detection of Synthetic Di- to Penta-Oligopeptides by Amine Derivatizations.

Chemical derivatizations have been extensively developed for highly sensitive detection of bioactive small peptides; however, their advantages from the viewpoint of longer oligopeptides remain unverified. In this study, electrospray-ionization (ESI)-mass spectrometric (MS) detection of synthetic di- to pentapeptides consisting of glycine and sarcosine were characterized by four amine derivatization methods. It was concluded that the ESI-MS detection of di- to pentapeptides was characterized by the molecular surface area of derivatized peptide moieties with an optimal value of 250 - 300 Å2, regardless of hydrophobicity and derivatization methods.

Baseline distribution and sources of selected agricultural runoff in the bottom water of an active cockle farming area, Bagan Pasir, Perak, Malaysia

This paper aims to study the spatial and temporal patterns of selected agricultural runoff, specifically in terms of glyphosate, nitrate, and ammonia in bottom water, as well as their possible sources, within an active cockle farming area in Bagan Pasir, Perak, Malaysia. Samples were taken along the cockle farming area from March to November 2019. Glyphosate was analyzed using HPLC with both extraction and derivatization methods using 9-fluorenyl-methyl chloroformate (FMOC-Cl), while nitrate and ammonia levels were determined using the standard Hach method. Generally, glyphosate, nitrate, and ammonia were present within the study site with the average concentration of 37.44 ± 12.27 μg/l, 1.65 ± 0.52 mg/l, and 0.37 ± 0.19 mg/l, respectively. The results suggest that glyphosate and nitrate might be derived from an inland source, while a uniform and low level of ammonia suggested might originate from lithogenic origins. Continuous monitoring remains encouraged.

NMR Analysis of Carboxylate Isotopomers of 13C-Metabolites by Chemoselective Derivatization with 15N-Cholamine.

A substantial fraction of common metabolites contains carboxyl functional groups. Their 13C isotopomer analysis by nuclear magnetic resonance (NMR) is hampered by the low sensitivity of the 13C nucleus, the slow longitudinal relaxation for the lack of an attached proton, and the relatively low chemical shift dispersion of carboxylates. Chemoselective (CS) derivatization is a means of tagging compounds in a complex mixture via a specific functional group. 15N1-cholamine has been shown to be a useful CS agent for carboxylates, producing a peptide bond that can be detected via 15N-attached H with high sensitivity in heteronuclear single quantum coherence experiments. Here, we report an improved method of derivatization and show how 13C-enrichment at the carboxylate and/or the adjacent carbon can be determined via one- and two-bond coupling of the carbons adjacent to the cholamine 15N atom in the derivatives. We have applied this method for the determination of 13C isotopomer distribution in the extracts of A549 cell culture and liver tissue from a patient-derived xenograft mouse.

Synthesis Candidates Herbicide Through Optimization Quinclorac Containing 3-Methyl-1H-pyrazol-5-yl.

To enhance quinclorac potency, twenty-five derivatives were synthesized containing 3-methyl-1H-pyrazol-5-yl by intermediate derivatization methods (IDMs). These compounds were confirmed by melting point (mp), 1HNMR, 13CNMR, and HRMS. The compound 1,3-dimethyl-1H-pyrazol-5-yl 3,7-dichloroquinoline-8-carboxylate (10a) was determined by X-ray diffraction. The activity of these compounds substituent on the phenyl was: electron-drawing group > neutral group > donor-drawing group, the results was like that of substituted benzyl group on pyrazole. The herbicidal activity assays showed that compounds 1-(2-fluorophenyl)-3-methyl-1H-pyrazol-5-yl 3,7-dichloroquinoline-8-carboxylate (8l, EC50 = 10.53 g/ha) and 10a (EC50 = 10.37 g/ha) had an excellent inhibition effect on barnyard grass in greenhouse experiment. Greenhouse safety experiment of rice exhibited almost no difference in plant height and fresh weight treated 10a at stage 1∼2-leaf of rice after 14 days but 8l had a detrimental effect. Two season field assays showed 10a herbicidal activity on barnyard grass at 150 g/ha as equal as 300 g/ha quinclorac in fields in 2019 and 2020. The study demonstrated that 10a could be further researched as a potential herbicide to control barnyard grass in fields.

A facile method for vancomycin C-terminus functionalization and derivatization through hydrazide

Over 60-year clinical use of vancomycin led to the emergence of vancomycin-resistant bacteria and threatened our health. To combat vancomycin-resistant strains, numerous vancomycin analogues were developed, such as Telavancin, Oritavancin and Dalbavancin. Extra structures embedded on C-terminus has been proved to be an effective strategy to promote antibacterial activity of vancomycin against vancomycin-resistant strains. Here, we reported a facile strategy, inspired by native chemical ligation, for vancomycin C-terminus functionalization and derivatization. The introduction of C-terminal hydrazide on vancomycin not only provided us an accessible method for C-terminus functionalization through carbonyl azide and thioester, also acted as an efficient site for vancomycin structure modifications. Based on hydrazide-vancomycin, we effectively conjugated cysteine and cysteine containing peptides onto vancomycin C-terminus, and two fluorescent FITC-vancomycin were prepared through Cys-Maleimide conjugation. Meanwhile, we introduced lipophilic structures onto vancomycin C-terminus via the hydrazide moiety. The obtained vancomycin derivatives were evaluated against both Gram-positive and negative bacteria strains.

Development of a green in-situ derivatization and deep eutectic solvent-based dispersive liquid–liquid microextraction method for analysis of short-chain fatty acids in beverage samples optimized by response surface methodology

An in-situ dispersive liquid–liquid microextraction and derivatization method based on deep eutectic solvent has been developed for the analysis of five short chain fatty acids (as model compounds) in different beverage samples prior to their determination by gas chromatography-flame ionization detection. In this method, 2-butanol was used as dispersive solvent derivatization reagent. For this purpose, the sample solution is transferred into a test tube and after dissolving sodium chloride in the solution, a suitable volume of HCl solution is added as catalyst. Thus, a mixture of 2-butanol and ethyl methyl ammonium chloride-carvacrol deep eutectic solvent (as an extraction solvent) is prepared and the mixture is quickly injected into the solution. The analytes are derivatized and extracted into the fine droplets of extracting agent, simultaneously. After centrifugation, an aliquot of the sedimented phase is injected into the separation system. Low limits of detection (0.89–6.6 µg L-1) and quantification (3.1–22.3 µg L-1) were obtained. Good repeatabilities with relative standard deviations ≤9.2% were obtained at the selected three concentrations. Also high enrichment factors, extraction recoveries, and enhancement factors were obtained within the ranges of 223–270, 76–92%, and 1074–1845, respectively. The developed method was successfully used in determination of the analytes in different beverage samples.

2-Phenoxyethanol derivatization in ink dating determination

Introduction 2-Phenoxyethanol (PE) is a volatile compound present in the composition of inks. After the deposition in a document, it starts to evaporate over time. This ageing process potentially allow to estimate the date of an ink in a document [1], however this is a complex system where the PE derivatization with different derivatization agents and methods can contribute to improve ink dating validation [2]. The aim of this work is to determine if PE derivatization with MSTFA:TMCS, will increase the sensitivity of the method contributing to the estimation of the ink age for a longer period of time. Materials and methods In order to compare peak resolution between PE and derivatized PE, a solution of 50 µg/ml of PE was prepared in hexane. The derivatized sample was prepared using chemical derivatization with MSTFA:TMCS (95:5) at a 80ºC during 30 min. The samples were analysed using GC/MS with an Agilent Technologies 5973 − 6890 N. GC MEGA-5 MS; 0.25µm, 0.32mm, 30 m capillary column was used. Chromatographic analysis was carried out under the following conditions: injection volume 2 µl, split ratio of 2:1 and injection temperature at 280 ºC. The oven temperature program starting at 90 ºC during 8 min, then ramped at 10 ºC min−1 to 100 ºC, and increased to 240 ºC at a rate of 30 ºC min−1 during 4.67 min. The MS analysis was carried out in SIM mode, which m/z of PE was 77, 94, 138 and PE-TMS was 151, 195, 210. Results The chromatogram results (Figure 1) showed that PE-TMS has a longer retention time (23.2 min) and a better resolution than PE (retention time of 13.2 min). Discussion and conclusions: This preliminary study showed an increase of the sensitivity of the PE-TMS. Our results revealed that PE derivatization with MSTFA:TMCS, might be useful in ink dating determination and can contribute to the decreasing of LOQ. However, more work has to be done. In conclusion, derivatization proves to be promising in the field of ink ageing, allowing getting sensitivity to estimate the age of an ink, in a long period of time. Figure 1. GC-MS chromatogram of PE (tr = 13.2) and PE-TMS (tr = 23.2) carried out in SIM mode using a GC MEGA-5 MS; 0.25µm, 0.32mm, 30 m capillary column.

Photodegradation of Molecular Iodine on SiO2 Particles: Influence of Temperature and Relative Humidity

AbstractA molecular derivatization method followed by gas chromatographic separation coupled with mass spectrometric detection was used to study photodegradation of molecular I2 adsorbed on solid SiO2 particles. The heterogeneous photodegradation of I2 was studied as a function of temperature and relative humidity in synthetic air to better understand its environmental fate. Two sets of experiments were carried out. In the first set of experiments, the temperature was T = (298 ± 1) K and relative humidity was varied from ≤ 2% to 75%RH under given experimental conditions. In the second set of experiments, the relative humidity within the Pyrex bulb was 40%RH and the temperature was varied from 283 ± 1 ≤ T (K) ≤ 323 ± 1. The obtained results show a considerably enhanced atmospheric lifetime of molecular iodine adsorbed on solid media that does not depend on relative humidity of the environment. The obtained results show that the rate constant for the photolysis of molecular iodine adsorbed on model SiO2 particles depends on temperature and is reported to be J (T)=(1.24 ± 1.4)×10−2×exp[(1482±345)/T]/s over the measured temperature range. The heterogeneous atmospheric residence time () of I2 adsorbed on solid media is calculated to range from 2 to 4.1 h. The experimentally obtained heterogeneous lifetime of I2 is shown to be considerably longer than its destruction by its principal atmospheric sink, photolysis. The observed enhanced atmospheric lifetime of I2 on heterogeneous media will likely have direct consequences on the atmospheric transport of I2 that influences the toxicity or the oxidative capacity of the atmosphere.

Derivatization of Sialylated Glycopeptides (DOSG) Enabling Site-Specific Isomeric Profiling Using LC-MS/MS.

Glycosylation is a ubiquitous and important post-translational modification, functioning as a critical role in many biological processes. Among all the monosaccharides, sialic acids are of utmost importance, due to their relatively high abundance and association with various diseases. Elucidation of linkage isomers on sialic acids remains challenging. Various chemical derivatization techniques have been developed to identify the linkage isomers of sialic acids on released N-glycans, such as esterification and alkylamidation. Here, we present an efficient, effective, and stable derivatization method that can discriminate α2,3- and α2,6-linked sialic acids on glycopeptides by generating mass difference of the isomers. A similar chemical method has been developed for released N-glycans. We adapted and optimized the method to be effectively utilized for the derivatization of glycopeptides. The method also efficiently derivatized the carboxylic groups on peptides in a controlled way, which was confirmed by MS/MS data. The efficient derivatization of the peptide backbone carboxylic groups prompts ca. 4.6-fold increase in signal. The method was employed to characterize sialylated glycopeptides derived from bovine fetuin, human alpha-1 acid glycoprotein (AGP), and human erythropoietin (EPO). The method effectively and reliably allowed the characterization of sialylated N- and O-glycopeptide isomers. For example, 11 sialylated glycans including 28 isoforms were well profiled on Asn72 of AGP. The method is facile and highly reproducible that targets site- and sialic acid linkage-specific profiling of glycosylation.

Mass spectrometry with derivatization method for concurrent measurement of amino acids and acylcarnitines in plasma of diabetic type 2 patients with diabetic nephropathy.

Amino acids (AAs) and acylcarnitines play a key role in metabolic disease and can be used as biomarkers of various diseases such as malignancies, type 2 diabetes (T2D), insulin resistance, and cardiovascular diseases, therefore, designing an accurate and simple laboratory method that simultaneously measure both groups of substances, could improve the process of analytes quantification. In this research, a flow injection tandem mass spectrometry (FI-MS/MS) method for simultaneous measurement of AAs and acylcarnitines in addition to results of validation is explained. Samples were mixed with internal standards and after derivatization (with butanolic-HCL), AAs, and acylcarnitines were quantified by tandem mass spectrometry (SCIEX API 3200). Analytical performance studies were designed based on the Clinical and Laboratory Standards Institute (CLSI) guidelines including precision, accuracy, linearity, and limit of detection-quantification (LOD-LOQ) experiments. Samples from patients with T2D in different stages of kidney disease were also analyzed to ensure the clinical usage of the method. Performance evaluation of the method demonstrated adequate results. The mean of estimated inter-assay precision (reported as a coefficient variation) for AAs and acylcarnitines were less than 8.7% and 12.3%, the estimated mean bias was below 8.8% and 10.2% respectively. LOD of analytes ranged between 0.6-10μmol per liter (μmol/L) for AAs and 0.02-1μmol/L for acylcarnitines. LOQ analytes showed a range of 2-25μmol/L and 0.05-5μmol/L for AAs and carnitine/acylcarnitines respectively. In diabetic patients sample analysis, a significant increase in acylcarnitines (C2, C4, C5DC, C6, C8, C10, C14) and citrulline with a significant decrease in valine were seen in patients with severely increased albuminuria. FI-MS/MS method with pre-injection derivatization with butanolic-HCL can be used for concurrent measurement of AAs and carnitine/acylcarnitines in a short time and it satisfies the analytical performance requirements. This method is applied for AAs and carnitine/acylcarnitines measurement in patient with T2DM and results show some of the acylcarnitines and AAs can be involved in diabetic nephropathy development. The online version contains supplementary material available at 10.1007/s40200-021-00786-3.

Fortuneicyclidins A and B, Pyrrolizidine Alkaloids with a 7-Azatetracyclo[5.4.3.0.02,8]tridecane Core, from Cephalotaxus fortunei.

Fortuneicyclidins A (1) and B (2), a pair of epimeric pyrrolizidine alkaloids containing an unprecedented 7-azatetracyclo[5.4.3.0.02,8]tridecane core, were isolated from the seeds of Cephalotaxus fortunei, along with two biogenetically relative known analogues, 3 and 4. The structures were determined by multiple spectral techniques and chemical derivatization methods. Compound 1 showed inhibitory activity against α-glucosidase.

Addition of Chloroprene Grignards to Aromatic Aldehydes: Synthesis of Homoallenyl Alcohols.

A general procedure for the one-pot synthesis of racemic homoallenyl alcohols from the corresponding aldehyde and chloroprene-derived Grignards is described. Employing bis[2-dimethylaminoethyl]ether (BDMAEE) as an additive at low temperatures shifts the selectivity of the chloroprene Grignard addition to aldehydes such that it is almost exclusive toward allene formation. In a set of follow-up experiments, simple and more elaborate methods for further derivatization have been demonstrated, allowing quick access to more complex structures.