Copper-Catalyzed Synthesis of Tetrasubstituted Olefins with Bicyclo[1.1.0]butanes and α-Diazo-Esters.

Palladium-Catalyzed One-Step Synthesis of Stereodefined Difunctionalized Glycals

A three-component Pd-catalyzed difunctionalization of internal and terminal alkynes with iodoperfluoroalkanes and boronic acids is reported here. Under low catalyst loading and mild reaction conditions, perfluoroalkylated tri- and tetrasubstituted olefins were obtained in very good yields and in excellent regio- and stereoselectivities.

A novel photocatalyzed trifluoromethylthio-trifluoromethylation of alkenes has been developed, using CF3SO2Na as both CF3 and SCF3 source. This photocatalyzed dual-oxidative strategy, which combine...

Seeking a sustainable and selective approach for terpene modification, a catalyst deconvolution approach was applied to the Meinwald rearrangement of (+)-limonene oxide as a model substrate to yield dihydrocarvone. In order to identify the most suitable catalyst and reaction conditions, different Lewis acids were evaluated. Bismuth triflate proved to be the most active catalyst under mild reaction conditions, with a low catalyst loading (1 mol%) and a relatively short reaction time (3 h). The optimized reaction conditions were subsequently transferred to other terpene-based epoxides, yielding different bio-based biscarbonyl structures, which constitute interesting and valuable substances, e.g. for polymer synthesis or as fragrances. Monoepoxides derived from (R)-(-)-carvone and (+)-dihydrocarvone rearranged to the desired products with high selectivities and yields. γ-Terpinene dioxide could be transformed in a double rearrangement to the respective biscarbonyl in moderate yields. A better result was achieved for limonene dioxide after further adjustment of the protocol to reach acceptable yields with a low catalyst loading of 0.1 mol% using 2-methyl tetrahydrofuran as a sustainable solvent. Compared to many procedures described in the literature, this procedure represents a step towards an increased sustainability in terpene modification by considering several principles of Green Chemistry, such as renewable resources, catalysis and mild reaction conditions for elementary chemical transformations. This article is part of a discussion meeting issue 'Science to enable the circular economy'.

Herein, an efficient, atom‐economic, environmentally benign catalytic protocol has been developed for synthesising ketones and aldehydes by acceptorless dehydrogenation of alcohols. The protocol employs C, C chelated Ir (III) NHC complexes to promote acceptorless dehydrogenation of both secondary and primary alcohols. Notably, oxidation of primary alcohol selectively yields the corresponding aldehyde where forming ester byproducts is possible. Using C, C chelated Ir (III) NHC complexes (0.1 mol%), and a catalytic amount of base t BuONa (5 mol%), several aliphatic and aromatic aldehydes and ketones including more challenging carbonyl compounds bearing heterocyclic rings were obtained in moderate to high yields. Moreover, the protocol is also efficient for synthesising industrially important molecules like heliotropin and 3,4,5‐trimethoxy acetophenone in moderate yields. Remarkably, the catalytic system allows the straightforward synthesis of the potentially bio‐active compound cholest‐4‐en‐3‐one through acceptorless dehydrogenation followed by double bond isomerisation under the reaction conditions. Low catalyst loading, mild reaction conditions, high selectivity, short reaction time, and broad‐substrate scopes are a few interesting characteristics of the catalytic protocol described herein.

[Reaction: see text] Tetrasubstituted olefins are readily prepared by the Pd-catalyzed cis addition of two aryl groups from an arylboronic acid to opposite ends of the triple bond of internal alkynes. The synthesis proceeds under very mild reaction conditions and tolerates a wide variety of functional groups, including alcohol, aldehyde, ester, TMS, and acetal groups.

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An efficient and facile method for the construction of tri- or tetrasubstituted exocyclic alkenes is achieved via a Cu(I)-catalytic system. This protocol exhibits mild conditions, low-cost catalyst, good functional group tolerance, and good yields. The selectivity toward tri- or tetrasubstituted alkenes can be delicately controlled by adjustment of base and solvent. A preliminary mechanism study manifested that the reaction undergoes a radical process, where B2pin2 plays an indispensable role.

Development of an air‐stable and cheap transition metal‐based catalyst for the formation of carbamates via the cross‐coupling reaction of various 2‐carbonyl substituted phenolic derivatives or 1,3‐diketo derivatives with N,N‐disubstituted formamides (C(sp2)O bond formation) under mild conditions is the key focus of synthetic chemists. In this context, we have developed a novel benzothiazole appended 2,6‐di picolinamide‐based Cu(II) complex for the facile generation of carbamates at a slightly elevated temperature (50°C) with a short reaction time and low catalyst loading (0.5 mol%) for the first time. The synthesized complex was well characterized by ultraviolet–visible, infrared, electron paramagnetic resonance spectroscopy, cyclic voltammetry, high‐resolution mass spectrometry (HRMS), as well as by single crystal X‐ray diffraction analysis. A wide range of aromatic carbamates was synthesized using complex 1 in good/excellent yield with decent functional group tolerance under mild conditions. Control experiments suggest that the reaction proceeds via the radical mechanism, and the formation of radical‐mediated intermediates was confirmed by the gas chromatography (GC), GCMS and HRMS. The use of low cost and environmentally benign catalysts in mild conditions along with the tolerance of a wide range of functional groups makes this an easy synthetic approach for the development of carbamates.

Aerobic oxidation of benzylic alcohols with bis(3,5-di- tert-butylsalicylaldimine)copper(II) complexes

Herein, we report the first example that P(O)-H species including H-phosphonates and H-phosphine oxides could participate in a highly regioselective 1,4-addition to in situ generated 1-benzopyrylium ion from C3-substituted 2H-chromene hemiketals, which provides a brand-new and effective approach for the synthesis of C4-phosphorylated 4H-chromenes with diverse C3-functionality (ketone, ester, sulfonyl, aryl, and alkyl groups). In total, the reaction features the use of inexpensive Zn(ClO4)2·6H2O as a catalyst, low catalyst loading (only 5 mol %), mild reaction conditions (60 °C, 10 min to 24 h), and broad substrate scope (46 examples) as well as good to high yields (>90% yield on average). More importantly, mechanistic experiments demonstrated the essential role of the C3-substituent on 2H-chromene hemiketals in stabilizing the in situ generated 1-benzopyrylium ion and the regioselective 1,4-addition control.

Diarylation of N- and O-nucleophiles through a metal-free cascade reaction

Organoselenium compounds, due to their high structural diversity, special function, and biological activities, have drawn attention in synthetic chemistry. Herein, a novel example of chiral N,N′-di...

Well-defined, air-stable Pd complexes of bis-phosphinoferrocene family of catalysts have been studied in the arylation of various ketones with aryl chlorides and aryl bromides. Bis(di-tert-butyl)phosphinoferrocene (DtBPF)-based catalysts such as (DtBPF)PdCl2 and (DtBPF)PdBr2 have been identified as two of the most active catalysts for the α-arylation of a model reaction involving propiophenone and 4-chlorotoluene. The scope of the (DtBPF)PdCl2 catalyst has been efficiently expanded to the arylation of various ketones with aryl chlorides and bromides with up to 97% isolated yields, under relatively mild reaction conditions at low catalyst loadings. The efficacy of the (DtBPF)PdCl2 catalyst was demonstrated at very low catalyst loadings with S/C 10,000 for the difficult aryl bromide, 4-bromoanisole, and 2000 for the electron-neutral aryl chloride, 4-chlorotoluene, on ∼10-g scale with excellent isolated yields and lower Pd in the product (6 and 48 ppm, respectively). Comparative studies on the Pd:DtBPF molar ratios between in situ catalysts and preisolated catalysts revealed that preisolated (DtBPF)PdX2 (X = Cl, Br) are the catalysts of choice due to various practical reasons.

The catalytic transformation of the most abundant cellulose to valuable platform chemicals is one of the significant issues to overcome the shortage of fossil fuels. Herein, we reported the first example of Ru-based homogeneous catalyst for the highly selective conversion of cellobiose and ball-milled cellulose to hexitols (including sorbitol, mannitol, and 1,4-sorbitan) under an acidic condition with the yield of 94.5% and 56.4%, respectively. The main features of this catalytic system were the high conversion efficiency of biomass, mild reaction condition (100 °C), and low catalyst loading, which was 1/20 of the related Ru/C heterogeneous catalyst. This work opened up a new avenue for the transformation of cellulose to hexitols under mild conditions.