Well compatible: The trifluoromethylations and perfluoroalkylations of aryl iodides some bromides with trifluoromethyl perfluoroalkylcopper(I) phenanthroline complexes occur broad scope at 25–50 °C (see scheme). complex is prepared from inexpensive reagents can be used in situ or isolated. reactions tolerate a range substituents also heteroaromatic systems. Detailed facts importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not...

Abstract Catalytic asymmetric carbon–carbon bond‐forming reactions provide one of the most efficient ways to synthesize optically active compounds, and, accordingly, many chiral catalysts for these have been developed in past two decades. However, efficiency terms turnover number (TON) is often lower than that some other reactions, such as hydrogenation, and this has obstacles industrial applications. Although there are difficulties increasing efficiency, issues might be solved by using...

A novel catalyst system based on complexes of calcium which promote the catalytic asymmetric 1,4-addition reactions and [3+2] cycloaddition α-amino acid derivatives with α,β-unsaturated carbonyl compounds have been developed. The proceeded smoothly in presence 5−10 mol % chiral to afford desired adducts high yields diastereo- enantioselectivities. wide range esters amides were applicable, other glycine even dl-alanine reacted several corresponding substituted pyrrolodine excellent In...

Catalytic asymmetric 1,4-addition and [3 + 2] cycloaddition reactions using chiral calcium species prepared from isopropoxide bisoxazoline ligands have been developed. Glycine Schiff bases reacted with acrylic esters to afford products, glutamic acid derivatives, in high yields enantioselectivities. During the investigation of reactions, we unexpectedly found that a occurred crotonate affording substituted pyrrolidine derivatives On basis this finding, investigated cycloadditions, it was...

The first highly diastereo- and enantioselective catalytic asymmetric 1,4-addition reactions of a glycine Schiff base to β-substituted α,β-unsaturated esters have been developed. reaction pathway was successfully controlled, the desired products were exclusively obtained with high enantioselectivities. product converted 3-substituted glutamic acid derivative by hydrolysis.

Salt of the earth: The first chiral, coordinative alkaline earth metal catalysts have been developed. These effectively promote catalytic asymmetric additions β-dicarbonyl compounds to nitroalkenes in high yields with enantioselectivities (up 96 %). Detailed facts importance specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by authors. Please note: publisher is responsible for content...

Chiral Ca-catalyzed asymmetric addition reactions of 3-substituted oxindoles with N-Boc-imines afford 3-tetrasubstituted oxindole derivatives bearing adjacent quaternary and tertiary chiral centers, which are key structures for biological activities. Ubiquitous nontoxic Ca catalysts (1–10 mol %) work well in this reaction, high yields (up to 99%) selectivities >99% ee) the products wide substrate scope have been attained. The intermediary enolates also discussed.

Recent developments in chiral alkaline-earth metal catalysts are summarized. Alkaline-earth metals very attractive species because they ubiquitous elements nature, and form less harmful compounds compared with heavy transition metals. Several types of ligands have been successfully employed for modification catalysts, high stereoselectivities achieved asymmetric carbon–carbon bond forming reactions. These remarkable results indicate that show promise as useful tools stereoselective synthesis.

A chiral calcium complex was found to be effective for the Mannich reactions of malonates with N-Boc imines. The desired adducts were obtained in excellent yields (up 95%) moderate good enantioselectivities 77% ee).

A chiral Ca catalyst based on CaCl(2) with a ligand was developed and applied to the asymmetric 1,4-addition of 1,3-dicarbonyl compounds nitroalkenes as model system. To address product inhibition issues, continuous flow heterogeneous catalyst. The system using newly synthesized, polymer-supported Pybox successfully employed, TON improved 25-fold compared those previous Ca(OR)(2) catalysts.

Abstract A current trend in organic chemistry is the development of highly efficient, environmentally friendly and inexpensive catalysts for asymmetric transformations. Alkaline earth metals, due to their specific chemical properties abundance nature, provide promising challenging synthesis. This article describes utilization alkaline metals an effective catalytic system based on calcium salts combination with Box‐type ligands. We disclose 1,4‐addition [3+2] cycloaddition reactions using...

Abstract Katalytische asymmetrische Kohlenstoff‐Kohlenstoff‐Kupplungen bieten einen der effizientesten Wege zu optisch aktiven Verbindungen, und entsprechend wurden in den vergangenen zwanzig Jahren viele chirale Katalysatoren für diese Reaktionen entwickelt. Diese sind, beispielsweise gemessen an ihrer Umsatzzahl (TON), oft weniger effizient als anderen Reaktionen, z. B. asymmetrischen Hydrierungen, was eines Hindernisse die industrielle Anwendung darstellte. Es existieren zwar einige...

Synthesis of β-nitrostyrene derivatives and their following reactions through two-step continuous-flow protocols with heterogeneous catalysts are described. In the first step to provide β-nitrostyrenes from aromatic aldehydes nitromethane, readily available amino-functionalized silica gel was employed as a catalyst gave products continuously for at least 100 h high selectivity. second step, β-nitrostyrenes, solid bases, immobilized acids, chiral supported metals nonmetals were used...

Abstract A one‐pot method for the synthesis of indoxyl derivatives starting from protected indole via indolin‐2,3‐acetonide as precursors is described. The are easy to handle, bench stable, and work indolin‐2,3‐diol surrogates. Substitution benzene ring give bromo‐, iodo‐, cyano‐, aryl‐, carbonyl‐derivatives also can be transformed into by acid hydrolysis. Furthermore, we demonstrate that modified act compounds because they converted parent indoles either or direct reduction.

Direct-type catalytic Mannich reactions of amides with imines proceeded smoothly using barium phenoxide as a catalyst to afford the desired adducts in high yields anti selectivities.

(±)‐Pregabalin, a γ‐amino acid derivative, has been synthesized by utilizing flow methods. A three‐step sequential‐flow reaction starting from commercial isovaleraldehyde and methyl malonate proceeded smoothly with heterogeneous catalysts to afford the precursor of pregabalin in yields 75–100 %, space‐time yield 52.2 g/L d was reached. In addition, catalyst for Knoevenagel reactions aldehydes malonates, which is first step synthesis, developed. Pregabalin finally obtained acid‐catalyzed...

Bis-hydrothiolation of alkynes providing anti-Markovnikov dithioacetals is reported. Lewis-acidic Ca(OSO2C4F9)2 (Ca(ONf)2) was synthesized for the first time and shown to be an excellent catalyst transformation. The reaction highly selective has a wide substrate scope. It revealed that vinyl sulfides were intermediates this transformation Ca(ONf)2 efficiently catalyzed unprecedented reactions unactivated with thiols afford in good high yields.

Ba black sheep: We have developed novel barium/binol catalysts prepared from alkaline earth metal amides and chiral binaphthol ligands. These effectively promoted the asymmetric Friedel–Crafts–type alkylation reactions of indoles with chalcone derivatives. This is first example using Brønsted bases. Detailed facts importance to specialist readers are published as "Supporting Information". Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by authors....

Out of the pybox: We have developed a novel chiral calcium iodide catalyst from CaI2 and pybox that is stable under moisture oxygen. This was applied to catalytic asymmetric Mannich-type reactions malonates with both N-Boc-protected aromatic aliphatic imines, resulted in moderate high yields enantioselectivities. To best our knowledge, this first example highly enantioselective metal-catalyzed imines. The Mannich adduct successfully converted into α-hydroxy β-amino acid derivative. also...

Abstract The unexpected reactions of indoline hemiaminals affords 2,5‐diaryl‐4‐hydroxythiazolines through a thioamidation/ring switch sequence. key to success this transformation is use thioamide as thiazoline precursor under transient tautomeric control. This features mild reaction conditions and good yields with broad functional group tolerance (17 examples, up 99 % yield). Further transformations the thiazolines provide direct entry dihydrothiazolo[4,5‐ b ]indoles thiazolo[4,5‐ ]indoles.