84666-30-8Relevant articles and documents
Synthesis of Optically Active N -(4-Hydroxynon-2-enyl)pyrrolidines: Key Building Blocks in the Total Synthesis of Streptomyces coelicolor Butanolide 5 (SCB-5) and Virginiae Butanolide A (VB-A)
Donges, Jonas,Hofmann, Sandra,Walter, Johannes C.,Reichertz, Julia,Brüggemann, Moritz,Frank, Andrea,Nubbemeyer, Udo
supporting information, p. 2632 - 2642 (2021/04/27)
Starting from 5-methylhexanal and (S)-configured N -propargylprolinol ethers, coupling delivered N -(4-hydroxynon-2-ynyl)prolinol derivatives as mixtures of C4 diastereomers. Resolution of the epimers succeeded after introduction of an (R)-mandelic ester derivative and subsequent HPLC separation. Alternatively, suitable oxidation gave the corresponding alkynyl ketone. Midland reagent controlled diastereoselective reduction afforded a defined configured propargyl alcohol with high selectivity. LiAlH 4reduction and Mosher analyses of the allyl alcohols enabled structure elucidation. The suitably protected products are used as key intermediates in enantioselective Streptomyces γ-butyrolactone signaling molecule total syntheses.
Total Synthesis of the Marine Macrolide Amphidinolide F
Ferrié, Laurent,Fenneteau, Johan,Figadère, Bruno
supporting information, p. 3192 - 3196 (2018/06/11)
A new and efficient convergent approach toward the synthesis of amphidinolide F is described through the assembly of three fragments. The two trans-tetrahydrofurans were built by a diastereoselective C-glycosylation with titanium enolate of bulky N-acetyloxazolidinethiones. The side chain was inserted by a Liebeskind-Srogl cross-coupling reaction. A sulfone condensation/desulfonylation sequence, a Stille cross-coupling, and a macrolactonization were applied to connect the fragments.
Versatile synthetic route to carbocyclic N-Acetylneuraminic acid and its derivatives
Mohan, Sankar,Thompson, John R.,Pinto, B. Mario,Bennet, Andrew J.
, p. 5213 - 5221 (2018/05/29)
Sialic acid (N-acetylneuraminic acid) is a carbohydrate that possess a nine carbon backbone, and it is often found at the termini of glycoconjugates in biological systems. Because of this prominence many syntheses have reported routes to sialic acid and m
Enantioselective Total Synthesis of (+)-Amphirionin-4
Ghosh, Arun K.,Nyalapatla, Prasanth R.
, p. 2296 - 2299 (2016/06/01)
An enantioselective total synthesis of (+)-amphirionin-4 has been accomplished in a convergent manner. The synthesis features an efficient enzymatic lipase resolution to access the tetrahydrofuranol core in optically active form. The functionalized tetrah
Palladium N-Heterocyclic Carbene Precatalyst Site Isolated in the Core of a Star Polymer
Bukhryakov, Konstantin V.,Mugemana, Clément,Vu, Khanh B.,Rodionov, Valentin O.
supporting information, p. 4826 - 4829 (2015/10/12)
An approach for supporting a Pd-NHC complex on a soluble star polymer with nanoscale dimensions is described. The resulting star polymer catalyst exhibits excellent activity in cross-coupling reactions, is stable in air and moisture, and is easily recoverable and recyclable. These properties are distinct and unattainable with the small-molecule version of the same catalyst.
Interligand interactions dictate the regioselectivity of trans-hydrometalations and related reactions catalyzed by [Cp?RuCl]. Hydrogen bonding to a chloride ligand as a steering principle in catalysis
Rummelt, Stephan M.,Radkowski, Karin,Ro?ca, Drago?-Adrian,Fürstner, Alois
supporting information, p. 5506 - 5519 (2015/05/13)
Reactions of internal alkynes with R3M-H (M = Si, Ge, Sn) follow an unconventional trans-addition mode in the presence of [Cp?Ru(MeCN)3]PF6 (1) as the catalyst; however, the regioselectivity is often poor with unsymmetrica
Non-Pd transition metal-catalyzed hydrostannations: Bu3SnF/PMHS as a tin hydride source
Maleczka Jr., Robert E.,Ghosh, Banibrata,Gallagher, William P.,Baker, Aaron J.,Muchnij, Jill A.,Szymanski, Amy L.
, p. 4000 - 4008 (2013/06/27)
Molybdenum, cobalt, nickel, ruthenium, and rhodium catalyzed alkyne hydrostannations using in situ generated Bu3SnH were studied. In most cases, Bu3SnF+polymethylhydrosiloxane (PMHS) performed well as the in situ source of Bu3/
Inactivation of Medium-Chain Acyl-CoA Dehydrogenase by a Metabolite of Hypoglycin: Characterization of the Major Turnover Product and Evidence Suggesting an Alternative Flavin Modification Pathway
Lai, Ming-tain,Li, Ding,Oh, Eugene,Liu, Hung-wen
, p. 1619 - 1628 (2007/10/02)
Medium-chain acyl-CoA dehydrogenase (MCAD) is a FAD-dependent enzyme that catalyzes the first step of the fatty acid oxidation cycle.When MCAD is exposed to (methylenecyclopropyl)acetyl-CoA (MCPA-CoA), a metabolite of hypoglycin A and the causative agent of Jamaican vomiting sickness, time-dependent inactivation follows with concomitant bleaching of the active-site FAD.Earlier studies have led to the postulation that the inactivation may involve a spontaneous ring fragmentation induced by a transient α-cyclopropyl radical, and thus suggest a one-electron oxidation pathway.In an effort to find more evidence for the proposed mechanism, we have isolated and characterized the major turnover product, a CoA ester consisting of a disubstituted terminal olefin, an epoxide, and a hydroxymethyl group, from the aerobic incubation mixture of MCPA-CoA and MCAD.Formation of this product may be initiated by trapping the acyclic radical intermediate with O2 to form a transient peroxy radical which, upon receiving one electron from flavin semiquinone followed by an intramolecular epoxidation, gives rise to the observed turnover product.The identification of such a highly oxygenated species as the major turnover product strongly sustains the intermediacy of a ring-opened radical, and as such, the departure from the expected inactivation may directly result from trapping of this radical intermediate by O2.This contention was subsequently substantiated by observing that the partition ratio is nearly 0 under anaerobic incubation.Interestingly, further investigation of the anaerobic inhibition resulted in the discovery of a minor inactivation pathway involving covalent modification of flavin at a locus other than the isoalloxazine ring.Although the chemical nature of the new inhibitor-coenzyme adduct(s) has yet to be elucidated, a structure having MCPA-CoA linked to the N(10) ribityl side chain is appealing.The mechanistic insights derived from this study provide compelling evidence supporting our early notion that inactivation of MCAD by MCPA-CoA is likely to proceed through a radical mechanism.
Palladium(0) Catalyzed Hydrostannylation of Alkynes. Stereospecific Syn Addition of Tributyltin Hydride
Miyake, Hideyoshi,Yamamura, Kimiaki
, p. 981 - 984 (2007/10/02)
Tetrakis(triphenylphosphine)palladium(0) catalyzes the hydrostannylation of alkynes to give vinylstannanes in excellent yields.This reaction proceeds in syn manner.
