50502-46-0

Upstream product

• 1189-09-9 methyl geranate 
• 1189-09-9 methyl geranate 

Downstream Products

• 87131-45-1 methyl (E)-6-tosyloxy-3-methyl-2-hexenoate 
• 173612-53-8 (+/-)-Se-phenyl 3-methyl-6-methoxymethyloxyocta-2E,7-dienselenoate 

Relevant academic research and scientific papers

Tailoring chemoenzymatic oxidation: Via in situ peracids

Epoxidation chemistry often suffers from the challenging handling of peracids and thus requires in situ preparation. Here, we describe a two-phase enzymatic system that allows the effective generation of peracids and directly translate their activity to the epoxidation of olefins. We demonstrate the approach by application to lipid and olefin epoxidation as well as sulfide oxidation. These methods offer useful applications to synthetic modifications and scalable green processes.

Synthesis and antiproliferative activity of new tonantzitlolone-derived diterpene derivatives

The synthesis of the diterpene (+)-tonantzitlolone A and a series of derivatives is reported. The study includes the determination of their antiproliferative activities against selected cancer cell lines.

An investigation into oxo analogues of molybdenum olefin metathesis complexes as epoxidation catalysts for alkenes

The oxo-imido molybdenum complex 2a is an effective catalyst at low catalyst loadings (0.5 mol % or below) for the epoxidation of a range of alkenes with tBuOOH in PhMe at 90 °C. Reactions are complete in less than 4 h and the products are isolated in high yields. The catalytic system is chemoselective for the epoxidation of electron-rich alkenes and allylic alcohols.

α,β-Unsaturated and cyclopropyl acyl radicals, and their ketene alkyl radical equivalents. Ring synthesis and tandem cyclisation reactions

Treatment of the α,β-unsaturated selenyl esters 12 and 14 with Bu3SnH-AIBN produces the corresponding 2-cyclohexenones 13 and 15 respectively via presumed α-ketene alkyl radical intermediates, viz. 10. By contrast, the 2,7-diene esters 34 and 39 undergo tandem radical cyclisations producing diquinanes, e.g. 38 (76%), and the corresponding allene-substituted α,β-unsaturated selenyl ester 48 gives the cyclooctadienone 56 on treatment with Bu3SnH-AIBN in refluxing benzene. The selenyl ester 19 derived from chrysanthemic acid produces a mixture of the γ,δ- unsaturated aldehyde 22 and the corresponding dimer 25a on treatment with Bu3SnH-AIBN. Furthermore, in the presence of methanol the only product from this reaction was the bis(methyl ester) dimer 25b, thereby lending further credence to the involvement of ketene alkyl radical intermediates in these reactions, and in the aforementioned reactions involving 2,6- and 2,7-diene selenyl esters. Treatment of the cyclopropane selenyl esters 59 and 61, containing keto- and oxy-group functionality in their side-chains, with Bu3SnH-AIBN led to excellent syntheses of the enol lactone 66 (76%) and the trans-fused bicyclo[6.1.0]nonane 67 (80-95%) respectively.

New synthetic models of cytochrome P450: How different are they from the natural species?

Soluble and matrix-bound P450 enzyme models have been synthesized carrying a SO3- ligand coordinating to iron. These complexes display features very similar to cofactors of enzymes such as P450cam with respect to electrochemistry and UV/Vis spectroscopy. Further they catalyze epoxidation reactions with turnover numbers up to 1800. DFT calculations revealed that the coordination of SO3- to Fe(III) produces an active species that displays allylic hydroxylation and epoxidation reactivity patterns that are nearly indistinguishable from those calculated for the natural active species of the enzyme cytochrome P450.

α-Ketene alkyl and α,β-unsaturated acyl radical intermediates in ring constructions

Treatment of the E-α,β-unsaturated selenyl esters and 1 and 3a with Bu3SnH-AIBN produces the corresponding cyclohexones 2 and 7/8 respectively via presumed α-ketene alkyl radical intermediates. In a similar manner the cyclopropyl ester 9 leads to a mixture of 12 and 13, and the 2,7-diene selenyl ester 15 undergoes a novel bi-cyclisation producing the diquinane 17 in 76% yield.

Regio- and Chemoselective Epoxidation of Fluorinated Monoterpenes and Sesquiterpenes by Dioxiranes

A comparative study on chemoselectivity of dimethyldioxirane (DMD) and methyl(trifluoromethyl)dioxirane (TFMD) in the epoxidation of trisubstituted C=C bonds presenting different activation in fluorinated monoterpene and sesquiterpene derivatives has been carried out.With respect to DMD, epoxidations performed with TFMD were faster under milder conditions, although high conversion yields were obtained with both reagents.In ease of epoxidation of unsaturated moieties the trend observed was: (CH3)(R1)C=CH(R2) ca. (CH3)(R1)C=CH(CH2OR) ca. (CH3)(R1)C=CF(R2) >> (CH3)(R1)C=CH(COOR) > (CF3)(R1)C=CH(R2).Results reported herein present the first example of direct epoxidation of a double bond bearing a CF3 substituent by non-biochemical means.Key Words: Epoxidation.Dimethyldioxirane; Methyl(trifluoromethyl)dioxirane.Chemoselectivity.Regioselectivity.Monoterpenes.Sesquiterpenes.

Synthesis of Pyridyl Terpenoid Ether Analogs of Juvenile Hormone

Some pyridyl terpenoid ether analogs of juvenile hormone were synthesized and tested for activity against stored-product insects.Compounds with a longer alkyl side chain were more active.