82294-38-0

Upstream product

• 1530-32-1 ethyltriphenylphosphonium bromide 
• 4736-60-1 ethyltriphenylphosphonium iodide 
• 1754-88-7 ethylenetriphenylphosphorane 
• 82294-33-5 1-trimethylsilyl ethylene triphenylphosphorane 

Downstream Products

• 29461-68-5 (Z)-2-iodo-3-phenylprop-2-ene 
• 354998-41-7 ((Z)-2-Iodo-propenyl)-cyclohexane 
• 1198439-57-4 (Z)-1-((5-iodohex-4-enyloxy)methyl)benzene 
• 1369589-13-8 (Z)-5-(2-iodoprop-1-enyl)-1,2,3-trimethoxybenzene 

Relevant academic research and scientific papers

Biomimetic synthesis of the shimalactones

A biomimetic synthesis of shimalactone A and B is described. Its key features are an unprecedented acid-catalyzed cyclization of a dienyl β-ketolactone and a Stille coupling/8π-6π electrocyclization cascade to create the oxabicyclo[2.2.1]heptane and bicyc

Studies toward the biomimetic total synthesis of (-)-PF-1018

Pericyclic reaction cascades are unparalleled in their ability to quickly generate complex structures with excellent stereocontrol. Herein, the use of a biomimetic Stille/8π electrocyclization/Diels-Alder cascade to successfully assemble the core structure of (-)-PF-1018 is reported.

A concise total synthesis of deoxyschizandrin and exploration of its antiproliferative effects and those of structurally related derivatives

The natural product deoxyschizandrin has been shown to have a wide range of biological activities. In recent years the therapeutic potential of this compound against cancers has attracted significant interest. Herein we describe a concise de novo total synthesis of deoxyschizandrin based around a double organocuprate oxidation strategy. In addition, we present the results of biological studies exploring the ability of deoxyschizandrin and synthetic precursors lacking the medium ring biaryl unit to inhibit the proliferation of a human cancer cell line. These studies led to the identification of a structurally novel agent with in vitro anticancer activity. Copyright

Asymmetrie construction of rings A - D of Daphnicyclidin-type alkaloids

[Chemical Equation Presented] The aza-Cope-Mannich reaction and ring-closing metathesis are key steps in the assembly of intermediates containing rings A - D of Daphniphyllum alkaloids of the daphnicyclidin type such as daphnipaxinin and oldhamine A.

Intermediates for the synthesis of polypropionate antibiotics

The invention relates to intermediate compounds of the formula wherein R1 is H or a protecting group, R2 and R3 each independently represent H, methyl, or a leaving group, provided that at least one, but not both, of Rsup

Biomimetic synthesis of (-)-longithorone A

An enantioseletive, biomimetic synthesis of (-)-longithorone A has been achieved using an intermolecular/transannular Diels-Alder sequence which provides some support for the proposed biosynthesis. The cycloaddition precursors were two [12]-paracyclophanes that were constructed with atropisomer control during ene-yne metathesis macrocyclizations. Copyright

Synthesis of epothilones, intermediates thereto, analogues and uses thereof

The present invention provides convergent processes for preparing epothilone A and B, desoxyepothilones A and B, and analogues thereof. Also provided are analogues related to epothilone A and B and intermediates useful for preparing same. The present invention further provides novel compositions based on analogues of the epothilones and methods for the treatment of cancer and cancer which has developed a multidrug-resistant phenotype.

A general strategy for the synthesis of cladiellin diterpenes: Enantioselective total syntheses of 6-acetoxycladiell-7(16),11-dien-3-ol (deacetoxyalcyonin acetate), cladiell-11-ene-3,6,7-triol, sclerophytin A, and the initially purported structure of sclerophytin A

Enantioselective total syntheses of the cladiellin diterpenes, 6-acetoxycladiell-7(16),11-dien-3-ol (deacetoxyalcyonin acetate, 6), cladiell-11-ene-3,6,7-triol (1), sclerophytin A (8), and tetracyclic diether 7, have been achieved by differential elaboration of tricyclic allylic alcohol 57. The central step in these syntheses is acid-promoted condensation of α,β-unsaturated aldehydes 45, 69 or 87, and cyclohexadienyl diol 44 to form, with complete stereocontrol, the hexahydroisobenzofuran core and five stereocenters of these cladiellin diterpenes. These syntheses also feature stereospecific photolytic deformylation α,γ-unsaturated aldehydes 46, 70, and 71 to remove the extraneous carbon introduced in the Prins-pinacol step; chemo- and stereoselective hydroxyl-directed epoxidation of 49, 72, and 90 followed by regioselective reductive opening with hydride to install the C3 tertiary hydroxyl group; and a diastereoselective Nozaki-Hiyama-Kishi cyclization of iodoaldehyde 56 to forge the oxacyclononane ring and the C6 hydroxyl stereocenter. Other key transformations include chemo- and stereoselective hydroxyl-directed epoxidation of tricyclic allylic alcohol 57 followed by regioselective reductive opening with hydride to install the C7 tertiary hydroxyl center of 1 and 8; chemo-, regio-, and stereoselective intramolecular oxymercuration-reductive demercuration of dienyl diol 62 to form the bridging tetrahydropyran ring of tetracyclic diether 7; and photochemical isomerization of the endocyclic double bond of 92 and 1 to give exocyclic congeners 7 and 8. The absolute stereochemistry of the synthetic products originates from two chiral nonracemic starting materials, (S)-(+)-carvone and (S)-(-)-glycidol. These syntheses define a versatile and concise strategy for the total synthesis of cladiellin diterpenes and provide additional illustrations of the uncommon utility of pinacol-terminated cationic cyclizations for the stereocontrolled synthesis of complex oxacyclic products.

Total Synthesis and Antitumor Activity of 12,13-Desoxyepothilone F: An Unexpected Solvolysis Problem at C15, Mediated by Remote Substitution at C21

A new epothilone analogue, 12,13-desoxyepothilone F (dEpoF, 21-hydroxy-12,13-desoxyepothilone B, 21-hydroxyepothilone D), was synthesized and evaluated for antitumor potential. A convergent strategy employed for the semipractical synthesis of 12,13-desoxyepothilone B (dEpoB) has been utilized to yield an amount of dEpoF sufficient for relevant biological studies. The results from an in vitro assay reveal that this new analogue is highly active against various tumor cell lines with a potency comparable to that of dEpoB. In particular, the growth of resistant tumor cells is inhibited by dEpoF at concentrations where paclitaxel (Taxol) is basically ineffective. A preliminary assessment of its in vivo activity is also promising. The new analogue, containing an additional hydroxyl group at C21, exhibits advantages over other epothilones in terms of water solubility, and can serve as a readily functionalizable handle to produce other useful compounds for pertinent biological studies.

Total synthesis of (+)-discodermolide

The total synthesis of (+)-discodermolide is described. The approach involves assemblage of three key stereotriad subunits through addition of nonracemic allenyltin, -indium, and -zinc reagents to (S)-3-silyloxy-2- methylpropanal derivatives, followed by reduction of the resulting anti,syn- or syn,syn-homopropargylic alcohol adducts to the (E)-homoallylic alcohols and subsequent Sharpless epoxidation. Addition of methyl cuprate reagents or Red-Al to the resultant epoxy alcohols yielded the key precursors, alkyne 4, aldehyde 9, and alcohol 24. Addition of alkyne 4 (as the lithio species 10) to aldehyde 9 afforded the propargylic alcohol 11 as the major stereoisomer. Lindlar hydrogenation and installation of appropriate protecting groups led to aldehyde 17. This was converted to the (Z)-vinylic iodide 18 upon treatment with α-iodoethylidene triphenylphosphorane. Suzuki coupling of this vinylic iodide with a boranate derived from iodide 25 led to the coupled product 27 with the complete carbon backbone of (+)-discodermolide and the correct stereochemistry. The synthesis was completed by cleavage of the cyclic PMP acetal at C1 with i-Bu2AlH and three-step oxidation - esterification to the ester 31. Cleavage of the C19 Et3Si ether and C19 carbamate formation followed by cleavage of the remaining alcohol protecting groups, first with DDQ and then aqueous HCl, afforded (+)-discodermolide (36).