Highly (regio)selective hydroformylation of olefins using self-assembling phosphines.

New phosphines with self-assembling 6-pyridinone moities were prepared, characterized, and examined in the hydroformylation of diverse olefins. Testing various known and novel ligands in the presence of [Rh(acac)(CO)2] under industrially relevant conditions, the hydroformylation of 1-octene proceeds best with 6,6'-(phenylphosphanediyl)bis(pyridin-2(1H)-one) (DPONP). Control experiments and modelling studies indicate dimerization of this ligand at higher temperatures (>100 °C). The optimal catalyst system is able to conserve high product linearity (>90%) for a broad range of olefins at industrially-employed temperatures at low ligand loading.

A General Concept for the Electronic and Steric Modification of 1-Metallacyclobuta-2,3-dienes: A Case Study of Group 4 Metallocene Complexes.

The synthesis of group 4 metal 1-metallacyclobuta-2,3-dienes as organometallic analogues of elusive 1,2-cyclobutadiene has so far been limited to SiMe3 substituted examples. We present the synthesis of two Ph substituted dilithiated ligand precursors for the preparation of four new 1-metallacyclobuta-2,3-dienes [rac-(ebthi)M] (M=Ti, Zr; ebthi=1,2-ethylene-1,10-bis(η5-tetrahydroindenyl)). The organolithium compounds [Li2(RC3Ph)] (1 b: R=Ph, 1 c: R=SiMe3) as well as the metallacycles of the general formula [rac-(ebthi)M(R1C3R2)] (2 b: M=Ti, R1=R2=Ph, 2 c: M=Ti, R1=Ph, R2=SiMe3; 3 b: M=Zr, R1=R2=Ph; 3 c: M=Zr, R1=Ph, R2=SiMe3) were fully characterised. Single crystal X-ray diffraction and quantum chemical bond analysis of the Ti and Zr complexes reveal ligand influence on the biradicaloid character of the titanocene complexes. X-band EPR spectroscopy of structurally similar Ti complexes [rac-(ebthi)Ti(Me3SiC3SiMe3)] (2 a), 2 b, and 2 c was carried out to evaluate the accessibility of an EPR active triplet state. Cyclic voltammetry shows that introduction of Ph groups renders the complexes easier to reduce. 13C CPMAS NMR analysis provides insights into the cause of the low field shift of the resonances of metal-bonded carbon atoms and provides evidence of the absence of the ß-C-Ti interaction.

Atroposelective Ir-Catalyzed C-H Borylation of Phthalazine Heterobiaryls.

The atroposelective iridium-catalyzed borylation of menthyloxy-substituted phthalazine heterobiaryls with diborons is reported. Utilizing [Ir(OMe)(COD)]2/2-aminopyridine as a rarely used efficient catalyst system, the heterobiaryls were selectively borylated in the 2-position of the carbocycle, exclusively yielding only one of the atropisomers, depending on the substitution of the phthalazine with (+)-menthyl or (-)-menthyl moieties. Exemplary further functionalization of a borylated atropisomer demonstrated that nickel-catalyzed Suzuki-Miyaura cross-coupling with an aryl halide was able to provide stereoretention to a certain degree (up to 75% de).

Bis(N-Heterocyclic Carbene) Manganese(I) Complexes: Efficient and Simple Hydrogenation Catalysts.

The use of bis(NHC) manganese(I) complexes 3 as catalysts for the hydrogenation of esters was investigated. For that purpose, a series of complexes has been synthesized via an improved two step procedure utilizing bis(NHC)-BEt3 adducts. By applying complexes 3 with KHBEt3 as additive, various aromatic and aliphatic esters were hydrogenated successfully at mild temperatures and low catalyst loadings, highlighting the efficiency of the novel catalytic system. The versatility of the developed catalytic system was further demonstrated by the hydrogenation of other substrate classes like ketones, nitriles, N-heteroarenes and alkenes. Mechanistic experiments and DFT calculations indicate an inner sphere mechanism with the loss of one CO ligand and reveal the role of BEt3 as cocatalyst.

Unusual selectivity in the ring-opening of γ-valerolactone oxide by amines.

Primary and secondary amines selectively react with the lactone moiety of γ-valerolactone oxide (GVLO). Several primary amines afforded the resulting epoxyamides with an intact epoxy group. In some cases addition of two equivalents of amine resulted in additional epoxide opening to give α,γ-dihydroxy-ß-amino-amides. The selective lactone-opening in GVLO was further corroborated by DFT-studies.

{µ-2,2'-(Ethane-1,2-di-yl)bis-[4,6-bis-(tri-methyl-sil-yl)-1,3-di-hydro-cyclo-penta-[c]pyrrol-5-one]}bis-[tri-carbonyl-iron(0)].

The binuclear title compound, [Fe2(C28H48N2O2Si4)(CO)6], consists of two central iron(0) atoms, each of them surrounded by a cyclo-penta-dienone moiety and three carbonyl ligands in a three-legged piano-stool shape. Furthermore, the bis-(cyclo-penta-dienone) ligand acts as a bridge between the two metal atoms.

Carbonyl-bis-{6,6'-[(3,3'-di-tert-butyl-5,5'-dimeth-oxy-1,1'-biphenyl-2,2'-di-yl)bis(oxy)]bis-(dibenzo[d,f][1,3,2]-dioxaphosphepine)}hydridorhodium(I) toluene-d 8 2.25-solvate.

The crystal-structure determination of the title compound, [RhH(C46H44O8P2)2(CO)]·2.25C7D8, is reported. The bis-phosphite ligand, C46H44O8P2, is well known as Biphephos. One specific characteristic of this hydrido rhodium(I) monocarbonyl complex is that one bis-phosphite ligand is coordinated in the expected bidentate mode and the other is coordinated in a monodentate mode. Thus, one phosphite moiety remains non-coordinating. All three coordinating phospho-rus atoms occupy the equatorial positions in the trigonal-bipyramidal environment around the rhodium atom. The crystals of the hydrido rhodium(I) monocarbonyl complex contains deuterated solvent mol-ecules (toluene-d 8). Most of them are included in the model, but the contributions of about 0.84 toluene per unit cell were removed from the diffraction data, using the SQUEEZE procedure in PLATON [Spek (2015 ▸). Acta Cryst. C71, 9-18].

Efficient Hydrogenation of N-Heterocycles Catalyzed by NNP-Manganese(I) Pincer Complexes at Ambient Temperature.

Manganese-catalyzed hydrogenation reactions have aroused widespread interest in recent years. Among the catalytic systems described, especially PNP- and NNP-Mn pincer catalysts have been reported for the hydrogenation of aldehydes, ketones, nitriles, aldimines and esters. Furthermore, NNP-Mn pincer compounds are efficient catalysts for the hydrogenolysis of less reactive amides, ureas, carbonates, and carbamates. Herein, the synthesis and application of specific imidazolylaminophosphine ligands and the corresponding Mn pincer complexes are described. These new catalysts have been characterized and studied by a combination of experimental and theoretical investigations, and their catalytic activities have been tested in several hydrogenation reactions with good to excellent performance. Especially, the reduction of N-heterocycles can be performed under very mild conditions.

Mono- and dinuclear zirconocene(iv) amide complexes for the catalytic dehydropolymerisation of phenylsilane.

The dehydropolymerisation of phenylsilane is investigated using group 4 metallocene amide complexes as catalysts. The dinuclear zirconocene amide complex Cp2Zr(NMe2)(µ-Me3SiC3SiMe3)Zr(NMe2)Cp2 (2) (Cp = η5-cyclopentadienyl) shows high activity in dehydrocoupling reactions, producing polyphenylsilanes with molecular weights ranging from 200 to 3000 g mol-1 and linear-to-cyclic product ratios of up to 80 : 20. Likewise, different ratios of oligomers and polymers with different tacticities could be described. Ansa-zirconocene amide complexes possessing the ebthi (ebthi = 1,2-ethylene-1,1'-bis(η5-tetrahydroindenyl)) ligand systems were prepared and evaluated for catalytic dehydropolymerisation in comparison to the dinuclear catalyst system.

Low-Valent Molybdenum PNP Pincer Complexes as Catalysts for the Semihydrogenation of Alkynes.

Low-valent molybdenum PNP pincer complexes were studied as catalysts for the semihydrogenation of alkynes. For that purpose, tBu-substituted PNP complexes PNP tBuMo(CO)2 (6a) and PNP tBuMo(CO)3 (6c) and the NNP complex NNP iPrMo(CO)2(PPh3) ((rac)-7) were synthesized and characterized. By utilizing the cyclohexyl-substituted complex PNPCyMo(CO)2(CH3CN) (5a), several diphenylacetylene derivatives are transformed to the corresponding (Z)-alkenes with good to very good diastereoselectivities (up to 91:9). Mechanistic experiments indicate an outer-sphere mechanism including metal-ligand cooperativity.

Revisiting Reduction of CO2 to Oxalate with First-Row Transition Metals: Irreproducibility, Ambiguous Analysis, and Conflicting Reactivity.

Construction of higher C≥2 compounds from CO2 constitutes an attractive transformation inspired by nature's strategy to build carbohydrates. However, controlled C-C bond formation from carbon dioxide using environmentally benign reductants remains a major challenge. In this respect, reductive dimerization of CO2 to oxalate represents an important model reaction enabling investigations on the mechanism of this simplest CO2 coupling reaction. Herein, we present common pitfalls encountered in CO2 reduction, especially its reductive coupling, based on established protocols for the conversion of CO2 into oxalate. Moreover, we provide an example to systematically assess these reactions. Based on our work, we highlight the importance of utilizing suitable orthogonal analytical methods and raise awareness of oxidative reactions that can likewise result in the formation of oxalate without incorporation of CO2. These results allow for the determination of key parameters, which can be used for tailoring of prospective catalytic systems and will promote the advancement of the entire field.

Synthesis of α-keto aldehydes via selective Cu(I)-catalyzed oxidation of α-hydroxy ketones.

An efficient approach to synthesize α-keto aldehydes was established through selective oxidation of α-hydroxy ketones catalyzed by Cu(I) using oxygen as oxidant. A wide array of α-keto aldehydes was prepared with isolated yields of up to 87%. The potential utilization of this reaction was evaluated by gram-scale reactions and synthetic applications.

A Selective and General Cobalt-Catalyzed Hydroaminomethylation of Olefins to Amines.

A new cobalt catalyst is presented for the domino hydroformylation-reductive amination reaction of olefins. The optimal Co-tert-BuPy-Xantphos catalyst shows good to excellent linear-to-branched (n/iso) regioselectivity for the reactions of aliphatic alkenes with aromatic amines under mild conditions. This system is far more selective than traditional cobalt(I) catalysts and even better than most known rhodium catalysts.

HCOOH disproportionation to MeOH promoted by molybdenum PNP complexes.

Molybdenum(0) complexes with aliphatic aminophosphine pincer ligands have been prepared which are competent for the disproportionation of formic acid, thus representing the first example so far reported of non-noble metal species to catalytically promote such transformation. In general, formic acid disproportionation allows for an alternative access to methyl formate and methanol from renewable resources. MeOH selectivity up to 30% with a TON of 57 could be achieved while operating at atmospheric pressure. Selectivity (37%) and catalyst performance (TON = 69) could be further enhanced when the reaction was performed under hydrogen pressure (60 bars). A plausible mechanism based on experimental evidence is proposed.

Palladium-Catalyzed Domino Aminocarbonylation of Alkynols: Direct and Selective Synthesis of Itaconimides.

The first direct and selective synthesis of substituted itaconimdes by palladium-catalyzed aminocarbonylation of alkynols is reported. Key to the success of this transformation is the use of a novel catalyst system involving ligand L11 and appropriate reaction conditions. In the protocol here presented, easily available propargylic alcohols react with N-nucleophiles including aryl- and alkylamines as well as aryl hydrazines to provide a broad variety of interesting heterocycles with high catalyst activity and excellent selectivity. The synthetic utility of the protocol is demonstrated in the synthesis of natural product 11 with aminocarbonylation as the key step. Mechanistic studies and control experiments reveal the crucial role of the hydroxyl group in the substrate for the control of selectivity.

Palladium-Catalyzed Cascade Carbonylation to α,ß-Unsaturated Piperidones via Selective Cleavage of Carbon-Carbon Triple Bonds.

A direct and selective synthesis of α,ß-unsaturated piperidones by a new palladium-catalyzed cascade carbonylation is described. In the presented protocol, easily available propargylic alcohols react with aliphatic amines to provide a broad variety of interesting heterocycles. Key to the success of this transformation is a remarkable catalytic cleavage of the present carbon-carbon triple bond by using a specific catalyst with 2-diphenylphosphinopyridine as ligand and appropriate reaction conditions. Mechanistic studies and control experiments revealed branched unsaturated acid 11 as crucial intermediate.

3,3-Difluoroallyl ammonium salts: highly versatile, stable and selective gem-difluoroallylation reagents.

The selective synthesis of fluorinated organic molecules continues to be of major importance for the development of bioactive compounds (agrochemicals and pharmaceuticals) as well as unique materials. Among the established synthetic toolbox for incorporation of fluorine-containing units, efficient and general reagents for introducing -CF2- groups have been largely neglected. Here, we present the synthesis of 3,3-difluoropropen-1-yl ammonium salts (DFPAs) as stable, and scalable gem-difluoromethylation reagents, which allow for the direct reaction with a wide range of fascinating nucleophiles. DFPAs smoothly react with N-, O-, S-, Se-, and C-nucleophiles under mild conditions without necessity of metal catalysts with exclusive regioselectivity. In this way, the presented reagents also permit the straightforward preparation of many analogues of existing pharmaceuticals.

Catalytic, Kinetic, and Mechanistic Insights into the Fixation of CO2 with Epoxides Catalyzed by Phenol-Functionalized Phosphonium Salts.

A series of hydroxy-functionalized phosphonium salts were studied as bifunctional catalysts for the conversion of CO2 with epoxides under mild and solvent-free conditions. The reaction in the presence of a phenol-based phosphonium iodide proceeded via a first order rection kinetic with respect to the substrate. Notably, in contrast to the aliphatic analogue, the phenol-based catalyst showed no product inhibition. The temperature dependence of the reaction rate was investigated, and the activation energy for the model reaction was determined from an Arrhenius-plot (Ea =39.6 kJ mol-1 ). The substrate scope was also evaluated. Under the optimized reaction conditions, 20 terminal epoxides were converted at room temperature to the corresponding cyclic carbonates, which were isolated in yields up to 99 %. The reaction is easily scalable and was performed on a scale up to 50 g substrate. Moreover, this method was applied in the synthesis of the antitussive agent dropropizine starting from epichlorohydrin and phenylpiperazine. Furthermore, DFT calculations were performed to rationalize the mechanism and the high efficiency of the phenol-based phosphonium iodide catalyst. The calculation confirmed the activation of the epoxide via hydrogen bonding for the iodide salt, which facilitates the ring-opening step. Notably, the effective Gibbs energy barrier regarding this step is 97 kJ mol-1 for the bromide and 72 kJ mol-1 for the iodide salt, which explains the difference in activity.

Correction: HCOOH disproportionation to MeOH promoted by molybdenum PNP complexes.

[This corrects the article DOI: 10.1039/D1SC04181A.].

1-Zirconacyclobuta-2,3-dienes: synthesis of organometallic analogs of elusive 1,2-cyclobutadiene, unprecedented intramolecular C-H activation, and reactivity studies.

The structure, bonding, and reactivity of small, highly unsaturated ring systems is of fundamental interest for inorganic and organic chemistry. Four-membered metallacyclobuta-2,3-dienes, also referred to as metallacycloallenes, are among the most exotic examples for ring systems as these represent organometallic analogs of 1,2-cyclobutadiene, the smallest cyclic allene. Herein, the synthesis of the first examples of 1-zirconacyclobuta-2,3-dienes of the type [Cp'2Zr(Me3SiC3SiMe3)] (Cp'2 = rac-(ebthi), (ebthi = 1,2-ethylene-1,1'-bis(η5-tetrahydroindenyl)) (2a); rac-Me2Si(thi)2, thi = (η5-tetrahydroindenyl), (2b)) is presented. Both complexes undergo selective thermal C-H activation at the 7-position of the ansa-cyclopentadienyl ligand to produce a new type of "tucked-in" zirconocene system, 3a and 3b, that possesses a η3-propargyl/allenyl ligand. Both types of complexes react with carbonyl compounds, producing enynes in the case of 2a and 2b, as well as η1-allenyl complexes for 3a and 3b. Computational analysis of the structure and bonding of 2a and 3a reveals significant differences to a previously described related Ti complex. All complexes were fully characterised, including X-ray crystallography and experimental results were supported by DFT analysis.