High iso Aldehyde Selectivity in the Hydroformylation of Short‐Chain Alkenes

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.     

Cameron–Liebler k-sets in subspaces and non-existence conditions

Designs, Codes and Cryptography - In this article we generalize the concepts that were used in the PhD thesis of Drudge to classify Cameron–Liebler line classes in PG $$(n,q), n\ge 3$$ , to...     

Kinematics of layered reinforced-concrete planar beam finite elements with embedded transversal cracking

In this work crack formation and development is addressed and implemented in a planar layered reinforced-concrete beam element. The crack initiation and growth is described using the strength criterion in conjunction with exact kinematics of the interlayer connection. In this way a novel embedded-discontinuity beam finite element is derived in which the tensile stresses in concrete at the crack position reaching the tensile strength will trigger a crack to open. Since the element is multi-layered, in this way the crack is allowed to propagate through the depth of the beam. The cracked layer(s) will involve discontinuity in the cross-sectional rotation equal to the crack-profile angle, as well as a discontinuity in the position vector of the layer’s reference line. A bond–slip relationship is superimposed onto this model in a kinematically consistent manner with reinforcement being treated as an additional layer of zero thickness with its own material parameters and a constitutive law implemented in the multi-layered beam element.     

An Isolable Radical Anion Featuring a 2-Center-3-Electron π-Bond without a Clearly Defined σ-Bond

Featuring an extra electron in the π* antibonding orbital, species with a 2-center-3-electron (2c3e) π bond without an underlying σ bond are scarcely known. Herein, we report the synthesis, isolation and characterization of a radical anion salt [K(18-C-6)]⁺{[(HCNDipp)₂Si]₂P₂}⋅⁻ (i.e. [K(18-C-6)]⁺ 3 ⋅⁻) (18-C-6=18-crown-6, Dipp=2,6-diisopropylphenyl), in which 3 ⋅⁻ features a perfectly planar Si₂P₂ four-membered ring. This species represents the first example of a Si- and P-containing analog of a bicyclo[1.1.0]butane radical anion. The unusual bonding motif of 3 ⋅⁻ was thoroughly investigated via X-ray diffraction crystallography, electron paramagnetic resonance spectroscopy (EPR), and calculations by density functional theory (DFT), which collectively unveiled the existence of a 2c3e π bond between the bridgehead P atoms and no clearly defined supporting P−P σ bond.     

Synergistic Peptide and Gold Catalysis: Enantioselective Addition of Branched Aldehydes to Allenamides

The combination of a peptide catalyst and a gold catalyst is presented for enantioselective addition reactions between branched aldehydes and allenamides. The two catalysts act in concert to provide γ,δ-enamide aldehydes bearing a fully substituted, benzylic stereogenic center – a structural motif common in many natural products and therapeutically active compounds – with good yields and enantioselectivities. The reaction tolerates a variety of alkyl and alkoxy substituted aldehydes and the products can be elaborated into several chiral building blocks bearing either 1,4- or 1,5- functional group relationships. Mechanistic studies showed that the conformational features of the peptide are important for both the catalytic efficiency and stereochemistry, while a balance of acid/base additives is key for ensuring formation of the desired product over undesired side reactions.     

Isolation and Total Synthesis of Kirkamide,an Aminocyclitol from an Obligate Leaf Nodule Symbiont

The new C₇N aminocyclitol kirkamide ( 1 ) was isolated from leaf nodules of the plant Psychotria kirkii by using a genome‐driven ¹H NMR‐guided fractionation approach. The structure and absolute configuration were elucidated by HRMS, NMR, and single‐crystal X‐ray crystallography. An enantioselective total synthesis was developed, which delivered kirkamide ( 1 ) on a gram scale in 11 steps and features a Ferrier carbocyclization and a Pd‐mediated hydroxymethylation. We propose that kirkamide is synthesized by Candidatus Burkholderia kirkii, the obligate leaf symbiont of Psychotria kirkii. Kirkamide ( 1 ) was shown to be toxic to aquatic arthropods and insects, thus suggesting that bacterial secondary metabolites play a protective role in the Psychotria/Burkholderia leaf nodule symbiosis.