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A convenient synthesis of several ‘phosphomide’ ligands (P adjacent to carbonyl group) from secondary phosphines is reported. The new anisoyl substituted phosphines are considerable more stable to hydrolysis, and are stronger σ-donor ligands than P-acetyl-diphenylphosphine as determined by the measurement of ν(CO) for the corresponding rhodium carbonyl complexes trans-[RhL2(CO)Cl]. In contrast, a new phosphomide derived from perfluoro-octanoyl chloride was found to be a highly unstable, electron poor π-acceptor ligand. The crystal structure of [RhCp*Cl2{Ph2PC(O)CH3}] showed a normal pseudo-octahedral piano-stool molecular geometry with a Rh&z.sbnd;P bond length of 2.3186(5) A˚. The extra stability observed for the P-anisoyl phosphomides has led us to apply this class of ligand in rhodium catalysed hydroformylation for the first time. [Copyright &y& Elsevier]

Rhodium catalysed hydroformylation of unsaturated esters has been studied. A pronounced temperature dependence was observed on the regioselectivity and catalytic activity for these reactions, and under the appropriate conditions, it is possible to obtain preferentially either linear or quaternary products. A quaternary selective hydroformylation of methyl atropate to give 1,3-aldehydic esters has also been developed. [Copyright &y& Elsevier]

Phospholane-phosphites are known to show highly unusual selectivity towards branched aldehydes in the hydroformylation of terminal alkenes. This paper describes the synthesis of hitherto unknown unsaturated phospholene borane precursors and their conversion to the corresponding phospholene-phosphites. The relative stereochemistry of one of these ligands and its Pd complex was assigned with the aid of X-ray crystal structure determinations. These ligands were able to approach the level of selectivity observed for phospholane-phosphites in the rhodium-catalysed hydroformylation of propene. High-pressure infra-red (HPIR) spectroscopic monitoring of the catalyst formation revealed that whilst the catalysts showed good thermal stability with respect to fragmentation, the C=C bond in the phospholene moiety was slowly hydrogenated in the presence of rhodium and syngas. The ability of this spectroscopic tool to detect even subtle changes in structure, remotely from the carbonyl ligands, underlines the usefulness of HPIR spectroscopy in hydroformylation catalyst development. [ABSTRACT FROM AUTHOR]

Wiley‐VCH, Weinheim 2016. 2 volumes, 702 pp., hardcover, € 299.00.—ISBN 978‐3527335527 [ABSTRACT FROM AUTHOR]

Starting from readily available allylglycine, a tandem hydroformylation-hemiaminal formation reaction has been developed for the synthesis of chiral functionalized piperidines, with very good diastereoselectivity and branched regioselectivity using Rh/(S,S,S)-BOBPHOS catalysts. Tandem hydroformylation-hemiacetal formation also proceeds with good diastereoselectivity (88:12), with the hemiacetal product being hydrogenated with retention of stereochemistry to give a chiral intermediate used in the synthesis of the new antibiotic nemonoxacin. [ABSTRACT FROM AUTHOR]

As an alternative to conventional asymmetric hydroformylation (AHF), asymmetric transfer hydroformylation (ATHF) by using formaldehyde as a surrogate for syngas is reported. A catalyst derived from commercially available [Rh(acac)(CO)2] (acac=acetylacetonate) and 1,2-bis[(2 S,5 S)-2,5-diphenylphospholano]ethane(1,5-cyclooctadiene) (Ph-BPE) stands out in terms of both activity and enantioselectivity. Remarkably, not only are high selectivities achievable, the reactions are very simple to perform, and higher enantioselectivity (up to 96 % ee) and/or turnover frequencies than those achievable by using the same catalyst (or other leading catalysts) can be obtained by using typical conditions for AHF. [ABSTRACT FROM AUTHOR]

The scope of carbon monoxide‐free Asymmetric Transfer HydroFormylation (ATHF) procedures using a highly active single catalyst system derived from 1,2‐bis‐((2,5)‐diphenylphospholano)ethane as chiral ligand has been studied. This reveals some highly successful reactions, but also significant limitations. The development of a new protocol in which a catalyst for formaldehyde decomposition to CO and H2 is combined with the catalyst of choice for the subsequent asymmetric hydroformylation is described. This enables ATHF reactions that were problematic to be significantly improved. The new method has been used in the synthesis of several key precursors to biologically active molecules. [ABSTRACT FROM AUTHOR]

The hydroformylation of propene to give predominantly iso‐butanal has been achieved; class‐leading selectivity is possible even at higher temperatures that deliver fast conversion. Racemic rhodium complexes of bidentate phospholane phosphites derived from tropos‐biphenols and unusual solvent systems are the key to the selectivity observed. [ABSTRACT FROM AUTHOR]

The hydroformylation of propene to give predominantly iso‐butanal has been achieved; class‐leading selectivity is possible even at higher temperatures that deliver fast conversion. Racemic rhodium complexes of bidentate phospholane phosphites derived from tropos‐biphenols and unusual solvent systems are the key to the selectivity observed. [ABSTRACT FROM AUTHOR]

This paper reports experimental and computational studies on the mechanism of a rhodium-catalyzed hydroformylation that is selective for branched aldehyde products from unbiased alkene substrates. This highly unusual selectivity relies on a phospholane-phosphite ligand prosaically called BOBPHOS. Kinetic studies using in situ high pressure IR (HPIR) and the reaction progress kinetic analysis methodology suggested two steps in the catalytic cycle were involved as turnover determining. Negative order in CO and positive orders in alkene and H2 were found and the effect of hydrogen and carbon monoxide partial pressures on selectivity were measured. Labeling studies found rhodium hydride addition to the alkene to be largely irreversible. Detailed spectroscopic HPIR and NMR characterization of activated rhodium-hydrido dicarbonyl species were carried out. In the absence of H2, reaction of the rhodiumhydrido dicarbonyl with allylbenzene allowed further detailed spectroscopic characterization of four- and five-coordinate rhodium-acyl species. Under single-turnover conditions, the ratios of branched to linear acyl species were preserved in the final ratios of aldehyde products. Theoretical investigations uncovered unexpected stabilizing CH-π interactions between the ligand and substrate which influenced the high branched selectivity by causing potentially low energy pathways to become unproductive. Energy span and degree of TOF control analysis strongly support experimental observations and mechanistic rationale. A three-dimensional quadrant model was built to represent the structural origins of regio- and enantioselectivity. [ABSTRACT FROM AUTHOR]

[Display omitted] • In situ spectroscopic study of hydroformylation catalysts at typical reaction concentrations. • Two ligands in the literature found to not coordinate to rhodium in the presence of syngas. • The highly active Rh/1,3,5,7-Tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane catalyst system studied by in situ HPIR spectroscopy and found to be mixture of resting states, with the composition tuneable by reaction conditions. The paper describes the composition of the resting states of several catalysts for alkene hydroformylation derived from bulky monophosphorus ligands. The results presented assess how bulky ligands compete with CO for the rhodium, and hence the role of 'unmodified' catalysts in alkene hydroformylation in the presence of these ligands. High Pressure Infra-Red (HPIR) spectroscopy was carried out at the rhodium and syngas concentrations typically used during catalysis experiments. These HPIR studies revealed that two ligands previously studied in Rh-catalysed hydroformylation react with [Rh(acac)(CO) 2 ] and H 2 /CO to give the unmodified rhodium cluster, [Rh 6 (CO) 16 ], as the only detectable species. Both less bulky phosphoramidites, and 1,3,5,7-Tetramethyl-6-phenyl-2,4,8-trioxa-6-phosphaadamantane, on the other hand, do not show the presence of [Rh 6 (CO) 16 ], and hence catalysis proceeds by purely ligand modified species under normal conditions. In the case of the Rh/phosphaadamantane catalysts, anecdotal evidence that this only forms a particularly useful catalyst above a certain pressure threshold can be understood in terms of how the catalyst composition varies with pressure. The ligands discussed have all been assessed in the hydroformylation of propene to separate their innate branched selectivity from their ability to isomerise higher alkenes to internal isomers. [ABSTRACT FROM AUTHOR]

An abstract of the article "Rapid Asymmetric Transfer Hydroformylation (ATHF) of Disubstituted Alkenes Using Paraformaldehyde as a Syngas Surrogate" by Rachael Pittaway and colleagues is presented.

Using the phospholane-phosphite ligand, BOBPHOS, almost perfect regioselectivities and high enantioselectivities (up to 92% ee) are observed in Rh catalysed enantioselective hydroformylation of vinyl arenes. This can be achieved under solvent-free conditions. [ABSTRACT FROM AUTHOR]