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Highly active catalysts of bisphosphine oxides for asymmetric Heck reaction

Bisphosphine oxides formed highly active asymmetric Heck catalysts, which were applied in asymmetric synthesis of pharmacologically active azacycles. Olefin insertion proceeded via cis pathways, different from P,N-ligands.

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Pyrroline – Wikipedia,
1-Pyrroline | C4H7N – PubChem

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An Expedient Synthesis of N-Acceptor-Substituted 2,3-Dihydropyrrols from the Corresponding 2-Pyrrolidinones

The title compounds 1 were prepared from the corresponding N-acceptor substituted 2-methoxypyrrolidines 3 by elimination with trimethylsilyl trifluoromethanesulfonate (TMSOTf) and N,N-di-iso-propyl ethyl amine (6 exampies, 57-84% yield). The enantiomerically pure N-methoxy-carbonyl protected elimination substrates 3aa and 3ab were synthesized from the L-pyroglutamic acid derived pyrrolidinones 6a and 6b in three steps (80-83% yield overall).

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Rhodium(III)-catalyzed C-H activation/annulation with vinyl esters as an acetylene equivalent

The behavior of electron-rich alkenes in rhodium-catalyzed C-H activation/annulation reactions is investigated. Vinyl acetate emerges as a convenient acetylene equivalent, facilitating the synthesis of sixteen 3,4-unsubstituted isoquinolones, as well as select heteroaryl-fused pyridones. The complementary regiochemical preferences of enol ethers versus enol esters/enamides is discussed.

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Pyrroline – Wikipedia,
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Manganese-Catalyzed Desaturation of N-Acyl Amines and Ethers

Enamines and enol ethers are versatile synthons for chemical synthesis. While several methods have been developed to access such molecules, prefunctionalized starting materials are usually required, and direct desaturation methods remain rare. Herein, we report direct desaturation reactions of N-protected cyclic amines and cyclic ethers using a mild I(III) oxidant, PhI(OAc)2, and an electron-deficient manganese pentafluorophenylporphyrin catalyst, Mn(TPFPP)Cl. This system displays high efficiency for alpha,beta-desaturation of various cyclic amines and ethers. Mechanistic probes suggest that the desaturation reaction occurs via an initial alpha-C-H hydroxylation pathway, which serves to protect the product from overoxidation.

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Pyrroline – Wikipedia,
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Catalytic, Cascade Ring-Opening Benzannulations of 2,3-Dihydrofuran O,O- and N,O-Acetals

An Al(OTf)3-catalyzed intramolecular cascade ring-opening benzannulation of 2,3-dihydrofuran O,O- and N,O-acetals is described. The cascade sequence involves the dihydrofuran ring-opening by acetal hydrolysis, an intramolecular Prins-type cyclization, and aromatization to generate an array of benzo-fused (hetero)aromatic systems in up to 95 % yield. This method represents the first example of dihydrofuran acetal usage in benzannulation reactions. The approach provides excellent regiocontrol based on the choice of alkenes used to form the requisite dihydrofuran acetals.

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One-pot synthesis of cyclic enecarbamates from lactam carbamates

A general, practical and efficient one-pot synthesis of cyclic enecarbamates is described. The protocol proceeds via reduction of lactam carbamate with Super-Hydride, followed by in situ dehydration with trifluoroacetic anhydride (TFAA) and diisopropylethylamine (DIPEA).

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PURINE DERIVATIVES USEFUL AS HSP90 INHIBITORS

The present application provides substituted purine derivatives and related compounds of the formulas shown. These compounds are useful as inhibitors of HSP90, and hence in the treatment of related diseases. (Formulae) Z1-Z3 , Xa-Xc, X2 , 324, Y and R are as defined in the specification

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A Catalytic Approach to Quinoline Fused Lactones and Lactams from Glycine Derivatives

A dual catalyst system [copper(II) chloride-sulfuric acid, (CuCl2-H2SO4)]-promoted aerobic oxidative reaction of glycine derivatives with 2,3-dihydrofurans or 2,3-dihydropyrroles has been explored, affording an efficient synthesis of high value quinoline fused lactones and lactams. The application of this new methodology to the synthesis of a bioactive C ring extension analogue of luotonin A has been accomplished in a concise three-step sequence.

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Pyrroline – Wikipedia,
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A short total synthesis of (¡À)-epimeloscine and (¡À)-meloscine enabled by a cascade radical annulation of a divinylcyclopropane

The first stereoselective synthesis of epimeloscine has been accomplished in 13 total steps with a longest linear sequence of 10 steps. The core of the synthesis takes only five steps, the key ones being acylation, stereoselective tandem radical cyclization of a divinylcyclopropane to make two rings, and group-selective ring-closing metathesis of the resulting divinylcyclopentane to make the last ring.

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Pyrroline – Wikipedia,
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Experimental and theoretical studies on the rotational barrier of 1-acyl- and 1-alkoxycarbonyl-2-pyrrolines

The conformational equilibrium as a result of the N-carbonyl bond rotation of several N-acyl- and N-alkoxycarbonyl-2-pyrrolines have been studied. The equilibrium constants and the rotational barriers were determined by theoretical methods (AM1, PM3, HF/3-21G(*) and HF/6-31G*) and, experimentally, by dynamic NMR (coalescence temperature). The measured rotational barriers for enecarbamates were found to be ca. 16 kcal mol-1 in C6D6 or C6D5NO2, whereas slightly higher values were found for enamides in C6D5NO2. Contrary to enamides, the rotational barriers for enecarbamates were not affected by changes in the polarity of the solvent employed.

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Pyrroline – Wikipedia,
1-Pyrroline | C4H7N – PubChem