114819-45-3

Upstream product

• 70681-41-3 (R)-dimethyl malate 

Downstream Products

• 112031-10-4 methyl (R)-2-(2,2-dimethyl-1,3-dioxolan-4-yl)acetate 
• 114784-20-2 (R)-4-benzyloxy-dihydro-2(3H)-furanone 
• 114784-19-9 (R)-Methyl 4-benzyloxy-3-hydroxybutanoate 
• 144754-24-5 methyl (R)-3-hydroxy-4-(triphenylmethyl)oxybutanoate 
• 58081-05-3 (R)-3-hydroxybutyrolactone 
• 159801-08-8 methyl (3R)-4-(tert-butyldiphenylsilyloxy)-3-hydroxybutanoate 
• 223429-10-5 methyl (3R)-3-hydroxy-4-{[(4-methylphenyl)sulfonyl]oxy}butanoate 
• 95310-94-4 (R)-(+)-4-bromo-3-hydroxybutyric acid ethyl ester 
• 327027-74-7 4-(tert-butyl-diphenyl-silanyloxy)-3-(4-methoxy-benzyloxy)-butyric acid methyl ester 
• 233609-25-1 (R)-3-Methoxy-4-trityloxy-butyric acid methyl ester 
• 1453486-55-9 methyl (R)-3-hydroxy-4-(4-methoxybenzyloxy)butanoate 
• 1453486-56-0 methyl (R)-3-(tert-butyldiphenylsilyloxy)-4-(4-methoxybenzyloxy)butanoate 
• 144754-25-6 (2S,3R) methyl 2--3-hydroxy-4-(triphenylmethoxy)-butanoate 
• 255040-39-2 (+)-(R)-methyl 3-((tert-butyldimethylsilyl)oxy)-4-(trityloxy)butanoate 

Relevant academic research and scientific papers

Chemical constituents and biological activities of Viburnum macrocephalum f. keteleeri

Three new compounds (1–3) and seven known compounds (4–10) have been isolated from the ethanolic extract of Viburnum macrocephalum f. keteleeri using bioactivity-guided fractionation and identified as methyl (2-α-L-rhamnopyranosyloxy)acetate (1), methyl (2R-3-α-L-rhamnopyranosyloxy)glycerate (2), methyl (3R-4-α-L-rhamnopyranosyloxy-3-hydroxy)butanoate (3), bridelionoside B (4), (6S,7E,9R)-roseoside (5), linarionoside A (6), 3,7,11-trimethyl-1,6-dodecadien-3,10,11-triol (7), (+)-8-hydroxylinalool (8), β-sitosterol (9) and daucosterol (10). The structures of 1–3, including absolute configurations, were determined by spectroscopic data (1H and 13C NMR, HSQC, HMBC and ORD) and chemical methods. In addition, compounds 1–8 were assayed for their insecticidal and antimicrobial activities. Compounds 7 and 8 exhibited moderately insecticidal effects against Mythimna separata with LD50 values of 180 and 230?μg?g?1, respectively. Compounds 2, 3, 7 and 8 showed varying antimicrobial activities with IC50 values ranging from 125 to 529?μM.

Metathesis-based synthesis of 3-methoxy α,β-unsaturated lactones: total synthesis of (R)-kavain and of the C1-C6 fragment of jerangolid D

The total synthesis of (R)-kavain and of the C1-C6 fragment of jerangolid D has been achieved in nine and seven steps, respectively, from commercially available dimethyl d-malate. A metathesis reaction of vinyl ethers and a sulfoxide-modified Julia olefination have been employed as the key steps.

ALIPHATIC AND AROMATIC GLUCOSIDES FROM ANOECTOCHILUS KOSHUNENSIS

A new simple aliphatic glucoside, 3-(R)-3-β-D-glucopyranosyloxybutanolide (kinsenoside) with its congeners and a heterocyclic aromatic glucoside, β-D-glucopyranosyl-3-pyridinemethanol (nicoloside) have been isolated from whole Anoectochilus koshunensis plants.Their structures were elucidated from chemical and spectroscopic evidence. Key Word Index: Anoectochilus koshunensis; Orchidaceae; 3,4-dihydroxy butanoic acid; glucoside; 3-glucosyloxybutanolide; kinsenoside; glucosyl-3-pyridinemethanol; nicoloside.

Asymmetric Synthesis of α,β-Unsaturated δ-Lactones through Copper(I)-Catalyzed Direct Vinylogous Aldol Reaction

A simple methodology for the asymmetric synthesis of chiral α,β-unsaturated δ-lactones was achieved by copper(I)-catalyzed direct vinylogous aldol reaction (DVAR) of β,γ-unsaturated esters and various aldehydes, including aromatic aldehydes, heteroaromatic aldehydes, α,β-unsaturated aldehydes, and aliphatic aldehydes. For aromatic and heteroaromatic aldehydes, a one-pot reaction consisting of DVAR, isomerization of the unsaturated carbon-carbon double bond from (E)-form to (Z)-form, and subsequent intramolecular transesterification was required to get the lactones in moderate to high yields with high enantioselectivity. For α,β-unsaturated and aliphatic aldehydes, the DVAR proceeded directly to afford the lactones in moderate yields with high enantioselectivity. In the DVAR, various functional groups were well tolerated. Moreover, the methodology was nicely applicable to the aldehyde group distributed in natural products, derivatives of natural product, and derivatives of drug molecules (atomoxetine and naproxen). The mechanism studies revealed that α-addition was reversible and not favored, which accounted for the excellent regioselectivity in the DVAR. The copper(I)-dienolate species generated through deprotonation was proposed to form an equilibrium with an allylcopper(I) species, which reacted with aldehydes to afford the DVAR products through a catalytic asymmetric allylation of aldehydes. Finally, the robustness of the present reaction was demonstrated by a gram-scale reaction, and the utility of the present methodology was showcased by the formal asymmetric synthesis of ezetimibe and fostriecin.

Phainanoids A-F, A new class of potent immunosuppressive triterpenoids with an unprecedented carbon skeleton from phyllanthus hainanensis

Phainanoids A-F (1-6), six highly modified triterpenoids with a new carbon skeleton by incorporating two unique motifs of a 4,5- and a 5,5-spirocyclic systems, were isolated from Phyllanthus hainanensis. Their structures with absolute configurations were determined by spectroscopic data, chemical methods, and X-ray crystallography. Compounds 1-6 exhibited exceptionally potent immunosuppressive activities in vitro against the proliferation of T and B lymphocytes. The most potent one, phainanoid F (6), showed activities against the proliferation of T cells with IC50 value of 2.04 ± 0.01 nM (positive control CsA = 14.21 ± 0.01 nM) and B cells with IC50 value of 1.60 ± 0.01 nM (CsA = 352.87 ± 0.01 nM), which is about 7 and 221 times as active as CsA, respectively. The structure-activity relationships of 1-6 are discussed.

Concise total synthesis of (-)-erinapyrone b from d-(+)-malic acid

A convenient and facile enantioselective synthesis of (-)-erinapyrone B from commercially available D-(+)-malic acid has been achieved in seven steps. One of the key steps in this synthesis was the one-pot reaction of palladium(II)-mediated Wacker-type oxidative cyclization in the presence of a catalytic amount of p-toluenesulphonic acid (p-TsOH) which has been found to be effective for the preparation of enantiopure 2,3-dihydro-4H-pyran-4-one from the corresponding enantiopure β-hydroxyenone via enantio-enriched diketohydroxy intermediate.

Studies directed towards the total synthesis of koshikalide: Stereoselective synthesis of the macrocyclic core

The stereoselective synthesis of the macrolactone core of the natural product koshikalide is described. Starting with readily available 1,4-butanediol and malic acid as synthons, our synthetic strategy involved the reiterative application of Gilman's reaction, Swern oxidation and Sharpless asymmetric epoxidation to establish the required stereocentres. Other key steps in the synthesis include Negishi cross coupling and Horner-Wadsworth-Emmons (HWE) reactions for construction of the main fragments. The 14-membered lactone ring was prepared by a selective Mitsunobu macrolactonization approach.

Synthesis of the C-18-C-34 fragment of amphidinolides C, C2, and C3

The C-18-C-34 fragment of amphidinolides C, C2, and C3 and the C-18-C-29 fragment of amphidinolide F have been constructed from a trans-2,5-disubstituted dihydrofuran. This key intermediate was prepared from a dihydrofuranone formed by diastereoselective rearrangement of a free or metal-bound oxonium ylide generated from a metal carbenoid. The side chains found in amphidinolides C and F were introduced using Sonogashira coupling reactions.

Stereoselective synthesis of tetrahydropyranyl diarylheptanoids (-)-centrolobine and (+)-centrolobine

A versatile chiron approach to the tetrahydropyranyl diarylheptanoid natural products (-)-centrolobine and (+)-centrolobine has been described. The use of an aldol reaction followed by reductive etherification for the formation of tetrahydropyran ring is of importance. Georg Thieme Verlag Stuttgart · New York.

NOVEL PRODRUGS OF STEROIDAL CYP17 INHIBITORS/ANTIANDROGENS

Prodrugs of C-17-heterocyclic- steroidal drugs providing improved oral bioavailability and phamacokinetics are described. The drugs are inhibitors of human CYP 17 enzyme, as well as potent antagonists of both wild type and mutant androgen receptors (AR), and are useful for the treatment of urogenital and/or androgen-related cancers, diseases and/or conditions, such as human prostate cancer, breast cancer, and prostate hyperplasia. The disclosure describes methods of synthesizing and using the prodrugs in cancer therapy.