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Stereoselective Olefination with Sterically Demanding Julia–Kocienski Reagents: Total Synthesis of Oxo-prothracarcin, Oxo-tomaymycin, and Boseongazepine B

ABSTRACT: Total syntheses of three pyrrolo[1,4]benzodiazepine anticancer

SUBMITTER: Leitis Z

PROVIDER: S-EPMC9434771 | biostudies-literature | 2022 Aug

REPOSITORIES: biostudies-literature

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Bromoacetate Olefination Protocol for Norbixin and Julia-Kocienski Olefination for Its Ester Syntheses.

Project description:A new olefination protocol utilizing ethyl bromoacetate was highlighted, in which magnesium enolate of the ester coupled with C20 dialdehyde 6, and double eliminations of the protected hydroxyl groups and bromine atoms of the coupling bromohydrin product, efficiently produced norbixin 1 after concomitant hydrolysis of the ester. A new (C7 + C10 + C7) disconnection approach was demonstrated for the synthesis of norbixin ethyl ester 2 by the Julia-Kocienski olefination of novel C7 benzothiazolyl-sulfone 11 and C10 2,7-dimethyl-2,4,6-octatrienedial (12).

| S-EPMC6648602 | biostudies-literature

E- or Z-Selective synthesis of 4-fluorovinyl-1,2,3-triazoles with fluorinated second-generation Julia-Kocienski reagents.

Project description:A highly modular approach to N-substituted 4-(1-fluorovinyl)triazoles is described. In situ desilylation and Cu-catalyzed ligation reaction of TMS-protected α-fluoropropargyl benzothiazole sulfone with aryl, alkyl, and metallocenyl azides furnished second-generation Julia-Kocienski reagents in good to excellent yields. Condensation reactions of these reagents with aldehydes can be tuned to yield E or Z-alkenes selectively. Under mild conditions with DBU as the base, reactions of aldehydes furnished E-alkenes as the major isomer. On the other hand, in condensation reactions with LHMDS as the base and in appropriate solvents, both aldehydes and ketones reacted to yield fluoroalkenes with Z-selectivity. Stereochemical assignment of E/Z olefins obtained in the reaction of a ketone with two Julia reagents was performed via X-ray crystallographic analysis and comparisons of NMR data. The method allows efficient and ready diversification of the N1-substituent and substituents at the double bond.

| S-EPMC4859785 | biostudies-literature

Regiospecifically Fluorinated Polycyclic Aromatic Hydrocarbons via Julia-Kocienski Olefination and Oxidative Photocyclization. Effect of Fluorine Atom Substitution on Molecular Shape.

Project description:A modular synthesis of regiospecifically fluorinated polycyclic aromatic hydrocarbons (PAHs) is described. 1,2-Diarylfluoroalkenes, synthesized via Julia-Kocienski olefination (70-99% yields), were converted to isomeric 5- and 6-fluorobenzo[c]phenanthrene, 5-and 6-fluorochrysene, and 9- and 10-benzo[g]chrysene (66-83% yields) by oxidative photocyclization. Photocyclization to 6-fluorochrysene proceeded more slowly than conversion of 1-styrylnaphthalene to chrysene. Higher fluoroalkene dilution led to a more rapid cyclization. Therefore, photocyclizations were performed at higher dilutions. To evaluate the effect of fluorine atom on molecular shapes, X-ray data for 5- and 6-fluorobenzo[c]phenanthrene, 6-fluorochrysene, 9- and 10-fluorobenzo[g]chrysene, and unfluorinated chrysene as well as benzo[g]chrysene were obtained and compared. The fluorine atom caused a small deviation from planarity in the chrysene series and decreased nonplanarity in the benzo[c]phenanthrene derivatives, but its influence was most pronounced in the benzo[g]chrysene series. A remarkable flattening of the molecule was observed in 9-fluorobenzo[g]chrysene, where the short 2.055 Å interatomic distance between bay-region F-9 and H-8, downfield shift of H-8, and a 26.1 Hz coupling between F-9 and C-8 indicate a possible F-9···H-8 hydrogen bond. In addition, in 9-fluorobenzo[g]chrysene, the stacking distance is short at 3.365 Å and there is an additional interaction between the C-11-H and C-10a of a nearby molecule that is almost perpendicular.

| S-EPMC4874880 | biostudies-literature

Rapid, stable, chemoselective labeling of thiols with Julia-Kocienski-like reagents: a serum-stable alternative to maleimide-based protein conjugation.

Project description: Not available

| S-EPMC3865870 | biostudies-literature

Sultones and Sultines via a Julia-Kocienski Reaction of Epoxides.

Project description:The development of the homologous Julia-Kocienski reaction has led to the discovery of two new reaction modes of epoxides with sulfones. These pathways allow rapid and direct access to a range of γ-sultones and γ-sultines.

| S-EPMC4691334 | biostudies-literature

Julia-Kocienski Approach to Trifluoromethyl-Substituted Alkenes<sup>1.</sup>

Project description:A Julia-Kocienski approach to trifluoromethyl-substituted alkenes was evaluated in the reactions of 1,3-benzothiazol-2-yl, 1-phenyl-1H-tetrazol-5-yl, and 1-tbutyl-1H-tetrazol-5-yl 2,2,2-trifluoroethyl sulfones with aldehydes. Among the various conditions tested, the best yields were obtained with 1-phenyl-1H-tetrazol-5-yl 2,2,2-trifluoroethyl sulfone, in CsF-mediated, room temperature olefinations in DMSO. Aromatic aldehydes gave (trifluoromethyl)vinyl derivatives in 23-86% yields, with generally moderate stereoselectivity. Straightforward synthesis of the Julia-Kocienski reagent, and conversion to trifluoromethyl-substituted alkenes under mild reaction conditions, are the advantages of this approach.

| S-EPMC4283945 | biostudies-literature

Synthesis of Chiral, Enantiopure Allylic Amines by the Julia Olefination of α-Amino Esters.

Project description:The four-step conversion of a series of N-Boc-protected l-amino acid methyl esters into enantiopure N-Boc allylamines by a modified Julia olefination is described. Key steps include the reaction of a lithiated phenylalkylsulfone with amino esters, giving chiral β-ketosulfones, and the reductive elimination of related α-acetoxysulfones. The overall transformation takes place under mild conditions, with good yields, and without loss of stereochemical integrity, being in this respect superior to the conventional Julia reaction of α-amino aldehydes.

| S-EPMC6273449 | biostudies-literature

Synthesis of Triarylsulfonium Salts with Sterically Demanding Substituents and Their Alkaline Stability.

Project description:As cationic functional groups with excellent alkaline resistance that are potentially applicable to building blocks of robust anion exchange membrane (AEM) materials for water splitting and fuel cell modules, we describe the synthesis of triarylsulfonium (TAS) salts bearing sterically demanding substituents by the reaction of arynes with diaryl sulfides/sulfoxides and by the Friedel-Crafts reaction of diaryl sulfoxides. The TAS cations possessing three substituted benzene rings, such as tris(2,5-dimethylphenyl)sulfonium and bis(2,5-dimethylphenyl)mesitylsulfonium, were effectively produced through the appropriate choice of reactions and reagents. The alkaline stability of the TAS cations thus obtained was evaluated from their time-course 1H NMR spectra in 1 M KOH/CD3OD, from which the alkaline resistance of the TAS cations increased dramatically as the steric bulkiness of the aromatic substituents attached to the TAS cations increased. Among them, bis(2,5-dimethylphenyl)mesitylsulfonium was found to exhibit 25 times higher alkaline resistance performance compared to benzyltrimethylammonium, a conventional quaternary ammonium cation. The decomposition mechanism of the TAS cations in the basic methanol media was studied in detail, and it was concluded that the decomposition occurred by the nucleophilic ipso-substitution by the methoxide anions.

| S-EPMC11894653 | biostudies-literature

Synthesis of Molybdenum and Tungsten Alkylidene Complexes That Contain Sterically Demanding Arenethiolate Ligands.

Project description:Imido alkylidene complexes of Mo and W and oxo alkylidene complexes of W that contain thiophenoxide ligands of the type S-2,3,5,6-Ph4C6H (STPP) and S-2,6-(mesityl)2C6H3 (SHMT = S-hexamethylterphenyl) have been prepared in order to compare their metathesis activity with that of the analogous phenoxide complexes. All thiolate complexes were significantly slower (up to ∼10× slower) for the metathesis homocoupling of 1-octene or polymerization of 2,3-dicarbomethoxynorbornene, and none of them was Z-selective. The slower rates could be attributed to the greater σ-donating ability of a thiophenoxide versus the analogous phenoxide and consequently a higher electron density at the metal in the thiophenoxide complexes.

| S-EPMC4195517 | biostudies-literature

Access to functionalized steroid side chains via modified Julia olefination.

Project description:Various functionalized steroidal side chains were conveniently accessed by a modified Julia olefination strategy using a common sulfone donor and an appropriate α-branched aldehyde acceptor. For the coupling of these hindered classes of reaction partners (and in contrast to typically observed trends), the benzothiazolyl(BT)-sulfone anion gave superior outcomes compared to the phenyltetrazolyl(PT)-sulfone anion.

| S-EPMC3045753 | biostudies-literature

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