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Asymmetric catalysis is an advanced area of chemical synthesis, but the handling of abundantly available, purely aliphatic hydrocarbons has proven to be challenging. Typically, heteroatoms or aromatic substructures are required in the substrates and reagents to facilitate an efficient interaction with the chiral catalyst. Confined acids have recently been introduced as tools for homogenous asymmetric catalysis, specifically to enable the processing of small unbiased substrates1. However, asymmetric reactions in which both substrate and product are purely aliphatic hydrocarbons have not previously been catalysed by such super strong and confined acids. We describe here an imidodiphosphorimidate-catalysed asymmetric Wagner-Meerwein shift of aliphatic alkenyl cycloalkanes to cycloalkenes with excellent regio- and enantioselectivity. Despite their long history and high relevance for chemical synthesis and biosynthesis, Wagner-Meerwein reactions utilizing purely aliphatic hydrocarbons, such as those originally reported by Wagner and Meerwein, had previously eluded asymmetric catalysis.

Despite the importance of rhodium complexes in catalysis, and the favorable 100% natural abundance of the spin-1/2 103Rh nucleus, there are few reports of 103Rh nuclear magnetic resonance (NMR) parameters in the literature. In part, this is the consequence of the very low gyromagnetic ratio of 103Rh and its dismal NMR sensitivity. In a previous paper [Harbor-Collins et al., J. Chem. Phys. 159, 104 307 (2023)], we demonstrated an NMR methodology for 1H-enhanced 103Rh NMR and demonstrated an application to the 103Rh NMR of the dirhodium formate paddlewheel complex. In this paper, we employ selective 18O labeling to break the magnetic equivalence of the 103Rh spin pair of dirhodium formate. This allows the estimation of the 103Rh–103Rh spin–spin coupling and provides access to the 103Rh singlet state. We present the first measurement of a 18O-induced 103Rh secondary isotope shift as well as the first instance of singlet order generated in a 103Rh spin pair. The field-dependence of 103Rh singlet relaxation is measured by field-cycling NMR experiments. [ABSTRACT FROM AUTHOR]

The nuclear magnetic resonance (NMR) spectroscopy of spin-1/2 nuclei with low gyromagnetic ratio is challenging due to the low NMR signal strength. Methodology for the rapid acquisition of 103Rh NMR parameters is demonstrated for the case of the rhodium formate "paddlewheel" complex R h 2 (H C O 2 ) 4 . A scheme is described for enhancing the 103Rh signal strength by polarization transfer from 1H nuclei, which also greatly reduces the interference from ringing artifacts, a common hurdle for the direct observation of low-γ nuclei. The 103Rh relaxation time constants T1 and T2 are measured within 20 min by using 1H-detected experiments. The field dependence of the 103Rh T1 is measured. The high-field relaxation is dominated by the chemical shift anisotropy mechanism. The 103Rh shielding anisotropy is found to be very large: |Δσ| = 9900 ± 540 ppm. This estimate is compared with density functional theory calculations. [ABSTRACT FROM AUTHOR]

Polyethylene (PE) is the most prevalent type of plastic waste and also the most challenging to depolymerize because of its inert carbon‐carbon (C−C) bonds.[1] High temperature and noble metals are usually required for depolymerization.[2] To avoid using noble metals, costly reagents and harsh reaction conditions, it is worthwhile but challenging to explore new reaction pathways.[3] We report an unprecedented mechanochemical reaction of PE and water to result in shorter‐chain alkanes, alkenes, alcohols, and ketones (Cn, where n≲50), with above 80 % of starting carbon converted into these products, which could be a valuable feedstock for re‐entering chemical value chains. This reaction is driven solely by ball milling, without heating and pressurizing. No costly catalysts are used. Instead, only earth‐abundant Al2O3 was milled with reactants. [ABSTRACT FROM AUTHOR]

This work reports the synthesis and structural study of a family of chlorotriarylbismuthonium salts. The abstraction of a chlorine atom with NaBArF from triarylbismuth dichloride species leads to monomeric and dimeric chlorotriarylbismuthonium species, which show a distinct behavior in solution and solid-state in comparison to their fluorotriarylbismuthonium analogues. [ABSTRACT FROM AUTHOR]

Recently developed polarisation transfer techniques are applied to the 103Rh nuclear magnetic resonance (NMR) of the 103Rh(acac)3 coordination complex in solution. Four-bond 1H – 103Rh J couplings of around 0.39 Hz are exploited to enhance the 103Rh NMR signal and to estimate the 103Rh T1 and T2 relaxation times as a function of field and temperature. The 103Rh longitudinal T1 relaxation in 103Rh(acac)3 is shown to be dominated by the spin–rotation mechanism, with an additional field-dependent contribution from the 103Rh chemical shift anisotropy. [ABSTRACT FROM AUTHOR]

Recently-developed polarisation-transfer techniques are applied to the 103Rh NMR of the Rh(acac)3 coordination complex in solution. Four-bond 1H-103Rh J-couplings of around 0.39 Hz are exploited to enhance the 103Rh NMR signal and to estimate the 103Rh T 1 and T 2 relaxation times as a function of field and temperature. The 103Rh longitudinal T 1 relaxation in Rh(acac)3 is shown to be dominated by the spin-rotation mechanism, with an additional field-dependent contribution from the 103Rh chemical shift anisotropy. [ABSTRACT FROM AUTHOR]

This article discusses a catalytic strategy for the conversion of isoxazoles and oxadiazoles into pyrazoles and 1,2,4-triazoles, respectively, through a formal O-to-N exchange. The protocol utilizes catalytic amounts of an air-stable Ni(4-CF3 stb) 3 complex in combination with hydrazine. The authors demonstrate the generality of the protocol and its functional group tolerance. This research provides a potential solution for the rapid evaluation of five-membered heterocyclic scaffolds in synthetic campaigns. [Extracted from the article]

The tremendous importance of dirhodium paddlewheel complexes for asymmetric catalysis is largely the result of an empirical optimization of the chiral ligand sphere about the bimetallic core. It was only recently that a H(C)Rh triple resonance 103Rh NMR experiment provided the long‐awaited opportunity to examine – with previously inconceivable accuracy – how variation of the ligands impacts on the electronic structure of such catalysts. The recorded effects are dramatic: formal replacement of only one out of eight O‐atoms surrounding the metal centers in a dirhodium tetracarboxylate by an N‐atom results in a shielding of the corresponding Rh‐site of no less than 1000 ppm. The current paper provides the theoretical framework that allows this and related experimental observations made with a set of 19 representative rhodium complexes to be interpreted. In line with symmetry considerations, it is shown that the shielding tensor responds only to the donor ability of the equatorial ligands along the perpendicular principal axis. Axial ligands, in contrast, have no direct effect on shielding but may come into play via the electronic cis ${cis}$ ‐effect that they exert onto the neighboring equatorial sites. On top of these fundamental interactions, charge redistribution within the core as well as the electronic trans ${trans}$ ‐effect of ligands of different donor strengths is reflected in the recorded 103Rh NMR shifts. [ABSTRACT FROM AUTHOR]