Regioselective Pd‐Catalyzed Methoxycarbonylation of Alkenes Using both Paraformaldehyde and Methanol as CO Surrogates

In recent years, considerable effort has focused on the development of novel carbonylative transformations using CO surrogates. Consequently, toxic CO gas can be replaced by more convenient inorganic or organic carbonyl compounds. Herein, the first regioselective methoxycarbonylation of alkenes with paraformaldehyde and methanol as CO substitutes is reported. This new procedure is applicable to a series of alkenes in the presence of a palladium catalyst under relatively mild conditions and is highly atom efficient.     

Alkenes in [2+2+2] Cycloadditions

Participation of alkenes and allenes in [2+2+2] cycloaddition reactions has attracted much attention recently. This version of the well‐established alkyne cyclotrimerization renders interesting products, such as cyclohexadienes and other polycycles, through cascade processes. Many mechanistic variations are observed when using certain metal complexes as catalysts. The frequent generation of stereogenic centers has prompted the development of efficient asymmetric versions. This Minireview summarizes the efforts reported to date on the use of double bonds as partners in [2+2+2] cyclotrimerizations.     

Catalytic Enantioselective Functionalization of Unactivated Terminal Alkenes

Terminal alkenes are readily available functional groups which appear in α‐olefins produced by the chemical industry, and they appear in the products of many contemporary synthetic reactions. While the organic transformations that apply to alkenes are amongst the most studied reactions in all of chemical synthesis, the number of reactions that apply to nonactivated terminal alkenes in a catalytic enantioselective fashion is small in number. This Minireview highlights the cases where stereocontrol in catalytic reactions of 1‐alkenes is high enough to be useful for asymmetric synthesis.     

Trifluoromethylation of Alkenes with Concomitant Introduction of Additional Functional Groups

The trifluoromethyl group is found in many synthetic bioactive compounds, and the difunctionalization of a C?C bond, as a powerful strategy for the construction of compounds with various functional groups, has been intensively investigated. Therefore, the difunctionalizing trifluoromethylation of alkenes has attracted growing interest because of the potential of the products as building blocks for bioactive molecules. In this review, we focus on recent advances in the trifluoromethylation of alkenes with concomitant introduction of additional functional groups.     

AuI-Catalyzed Haloalkynylation of Alkenes

The formal insertion of alkenes into aromatic chloro- and bromoalkynes takes place under cationic gold catalysis. This haloalkynylation reaction can be performed with cyclic, gem-disubstituted and monosubstituted alkenes, using BINAP, triazolo[4,3-b]isoquinolin-3-ylidene ligands or SPhos, respectively. The products were isolated in moderate to excellent yields and with complete diastereo- and regioselectivity; the halogen atom bonding the more substituted carbon of the alkene. Preliminary experiments showed that the enantioselective haloalkynylation of cyclopentene can be performed with (S)-BINAP to afford the insertion products with moderate to good enantioselectivities.     

Copper-Catalyzed Defluorinative Hydroarylation of Alkenes with Polyfluoroarenes

A catalytic defluorinative hydroarylation of alkenes with polyfluoroarenes in the presence of dppbz-ligated Cu catalyst and silanes was developed. This method provides a straightforward and alternative avenue to synthetic important polyfluorinated arenes with readily available and bench-stable alkenes as latent nucleophiles, and therefore avoids conventional reliance on stoichiometric quantities of organometallic reagents. This reaction proceeds under very mild conditions and exhibits good functional group compatibility and high level of regioselectivity. The synthetic potential of this method was further demonstrated by a gram-scale synthesis, and an array of experimental studies were also carried out to elaborate the probable mechanism.     

Manganese-Catalyzed Hydroarylation of Unactivated Alkenes

Transition-metal-catalyzed hydroarylation of unactivated alkenes with strategic use of remote coordinating functional groups has received significant attention recently to address the issues of both low reactivity and poor selectivity. The bidentate 8-aminoquinoline amide group is the most successfully adopted in unactivated alkenes for Pd and Ni catalysis. We describe the first manganese-catalyzed hydroarylation of unactivated alkenes bearing diverse simple functionalities with arylboronic acids. A series of δ- and γ-arylated amides, ketones, pyridines, and amines was accessed with excellent regioselectivity and in high yields. Hydroalkenylation of unactivated alkenes was also shown to be applicable under this manganese-catalysis regime. The method features earth-abundant manganese catalysis, easily available substrates, broad functional-group tolerance, and excellent regioselective control.     

Evolution of carbonylation catalysis: no need for carbon monoxide

Progress in organometallic catalysis began with the discovery of the Roelen reaction (hydroformylation with carbon monoxide and hydrogen) in 1938 and the Reppe reaction (hydrocarboxylation with carbon monoxide and water) in 1939. Since then, carbonylation chemistry by using carbon monoxide has occupied a central position in organometallic chemistry, as it relates to organic synthesis. There is, however, the problem of using gaseous carbon monoxide (a toxic greenhouse gas) in this chemistry. Recently, some strategies that address this issue have appeared. This minireview describes carbonylation reactions that can be conducted without the direct use of carbon monoxide. These carbonylation reactions provide reliable and accessible tools for synthetic organic chemists.     

Perfluoroalkylation of Unactivated Alkenes with Acid Anhydrides as the Perfluoroalkyl Source

An efficient perfluoroalkylation of unactivated alkenes with perfluoro acid anhydrides was developed. Copper salts play a crucial role as a catalyst to achieve allylic perfluoroalkylation with the in situ generated bis(perfluoroacyl) peroxides. Furthermore, carboperfluoroalkylation of alkene bearing an aromatic ring at an appropriate position on the carbon side chain was found to proceed under metal‐free conditions to afford carbocycles or heterocycles bearing a perfluoroalkyl group. This method, which makes use of readily available perfluoroalkyl sources, offers a convenient and powerful tool for introducing a perfluoroalkyl group onto an sp³ carbon to construct synthetically useful skeletons.     

Manganese‐Catalyzed Hydroarylation of Unactivated Alkenes

Transition‐metal‐catalyzed hydroarylation of unactivated alkenes with strategic use of remote coordinating functional groups has received significant attention recently to address the issues of both low reactivity and poor selectivity. The bidentate 8‐aminoquinoline amide group is the most successfully adopted in unactivated alkenes for Pd and Ni catalysis. We describe the first manganese‐catalyzed hydroarylation of unactivated alkenes bearing diverse simple functionalities with arylboronic acids. A series of δ‐ and γ‐arylated amides, ketones, pyridines, and amines was accessed with excellent regioselectivity and in high yields. Hydroalkenylation of unactivated alkenes was also shown to be applicable under this manganese‐catalysis regime. The method features earth‐abundant manganese catalysis, easily available substrates, broad functional‐group tolerance, and excellent regioselective control.     

Gallium‐Assisted Transfer Hydrogenation of Alkenes

We report a rare case of alkene transfer hydrogenation using a main‐group compound instead of a transition‐metal complex as catalyst. We disclosed that 1,4‐cyclohexadiene can be used as H₂ surrogate towards olefin reduction in the presence of [IPrGaCl₂][SbF₆]. Hydrogenative cyclizations have also been carried out because this cationic gallium complex is also a potent hydroarylation catalyst.     

Asymmetric Epoxidation of Non-Functionalized Alkenes Using Transition Metal Complexes

Asymmetric catalytic epoxidation of alkenes such as styrenes, chromenes and indene using transition metal complexes both inhomogeneous and heterogeneous phase has been discussed in this review. The various strategies to make the catalysts recyclable by introducing in-built phase transfer ability, converting these to dimeric form, exchanging into clays and supporting on polymeric or inorganic supports are discussed at length.     

Manganese‐Catalyzed Hydrofunctionalization of Alkenes

The manganese‐catalyzed hydrosilylation and hydroboration of alkenes has been developed using a single manganese(II) precatalyst and reaction protocol. Both reactions proceed with excellent control of regioselectivity and in high yields across a variety of sterically and electronically differentiated substrates (25 examples). Alkoxide activation, using NaO^tBu, was key to precatalyst activation and reactivity. Catalysis was achieved across various functional groups and on gram‐scale for both the developed methodologies with catalysts loadings as low as 0.5 mol %.     

Carbonylation of Alkynes,Alkenes and Alcohols using Metal Complex Catalysts

Carbonylation of olefins, alcohols and halides using homogeneous as well as heterogeneous catalysts has been discussed. Highlights of contributions on the activity, selectivity and stability of catalysts for carbonylation reactions are discussed. Kinetics and mechanism including characterization of the intermediate catalytic species has also been reviewed. The performance of anchored Pd complexes on mesoporous supports (MCM-41 and MCM-48), water soluble Pd complexes and supported Pd catalysts in carbonylation of aryl alcohols and olefins has been discussed in the context of catalyst-product separation. Some aspects of kinetic modelling and reaction engineering of these multiphase catalytic reactions have also been reviewed.     

Zirconium-Catalyzed Atom-Economical Synthesis of 1,1-Diborylalkanes from Terminal and Internal Alkenes

A general and atom-economical synthesis of 1,1-diborylalkanes from alkenes and a borane without the need for an additional H₂ acceptor is reported for the first time. The key to our success is the use of an earth-abundant zirconium-based catalyst, which allows a balance of self-contradictory reactivities (dehydrogenative boration and hydroboration) to be achieved. Our method avoids using an excess amount of another alkene as an H₂ acceptor, which was required in other reported systems. Furthermore, substrates such as simple long-chain aliphatic alkenes that did not react before also underwent 1,1-diboration in our system. Significantly, the unprecedented 1,1-diboration of internal alkenes enabled the preparation of 1,1-diborylalkanes.     

Palladium‐Catalyzed Hydroamidocarbonylation of Olefins to Imides

Carbonylation reactions allow the efficient synthesis of all kinds of carbonyl‐containing compounds. Here, we report a straightforward synthesis of various imides from olefins and CO for the first time. The established hydroamidocarbonylation reaction affords imides in good yields (up to 90 %) and with good regioselectivity (up to 99:1) when applying different alkenes and amides. The synthetic potential of the method is highlighted by the synthesis of Aniracetam by intramolecular hydroamidocarbonylation.     

Iron-Catalyzed Highly Enantioselective cis-Dihydroxylation of Trisubstituted Alkenes with Aqueous H2O2

Reliable methods for enantioselective cis-dihydroxylation of trisubstituted alkenes are scarce. The iron(II) complex cis-α-[Fe^II(2-Me₂-BQPN)(OTf)₂], which bears a tetradentate N₄ ligand (Me₂-BQPN=(R,R)-N,N′-dimethyl-N,N′-bis(2-methylquinolin-8-yl)-1,2-diphenylethane-1,2-diamine), was prepared and characterized. With this complex as the catalyst, a broad range of trisubstituted electron-deficient alkenes were efficiently oxidized to chiral cis-diols in yields of up to 98 % and up to 99.9 % ee when using hydrogen peroxide (H₂O₂) as oxidant under mild conditions. Experimental studies (including ¹⁸O-labeling, ESI-MS, NMR, EPR, and UV/Vis analyses) and DFT calculations were performed to gain mechanistic insight, which suggested possible involvement of a chiral cis-Fe^V(O)₂ reaction intermediate as an active oxidant. This cis-[Fe^II(chiral N₄ ligand)]²⁺/H₂O₂ method could be a viable green alternative/complement to the existing OsO₄-based methods for asymmetric alkene dihydroxylation reactions.     

Use of Formic Acid as a CO Surrogate for the Reduction of Nitroarenes in the Presence of Dienes: A Two-Step Synthesis of N-Arylpyrroles via 1,2-Oxazines

Formic acid, activated by acetic anhydride and a base, was employed as a CO surrogate to deoxygenate nitroarenes to nitrosoarenes, a reaction catalyzed by a palladium/phenanthroline complex in the homogeneous phase. Nitrosoarenes were trapped by conjugated dienes to give 3,6-dihydro-2H-[1,2]-oxazines. The latter were then transformed into N-arylpyrroles employing CuCl as the catalyst. The reaction was designed to give the best results for pyrroles lacking any substituent in the 2 and 5 positions, which are difficult to produce employing most pyrrole syntheses.