More Like this

1. Self-Amplified HF Release and Polymer Deconstruction Cascades Triggered by Mechanical Force

   https://doi.org/10.1021/jacs.4c01402  

   Hu, Yixin; Wang, Liqi; Kevlishvili, Ilia; Wang, Shu; Chiou, Chun-Yu; Shieh, Peyton; Lin, Yangju; Kulik, Heather J.; Johnson, Jeremiah A.; Craig, Stephen L. (April 2024, Journal of the American Chemical Society)

   Hydrogen fluoride (HF) is a versatile reagent for material transformation, with applications in self-immolative polymers, remodeled siloxanes, and degradable polymers. The responsive in situ generation of HF in materials therefore holds promise for new classes of adaptive material systems. Here, we report the mechanochemically coupled generation of HF from alkoxy-gem-difluorocyclopropane (gDFC) mechanophores derived from the addition of difluorocarbene to enol ethers. Production of HF involves an initial mechanochemically assisted rearrangement of gDFC mechanophore to α-fluoro allyl ether whose regiochemistry involves preferential migration of fluoride to the alkoxy-substituted carbon, and ab initio steered molecular dynamics simulations reproduce the observed selectivity and offer insights into the mechanism. When the alkoxy gDFC mechanophore is derived from poly(dihydrofuran), the α-fluoro allyl ether undergoes subsequent hydrolysis to generate 1 equiv of HF and cleave the polymer chain. The hydrolysis is accelerated via acid catalysis, leading to self-amplifying HF generation and concomitant polymer degradation. The mechanically generated HF can be used in combination with fluoride indicators to generate an optical response and to degrade polybutadiene with embedded HF-cleavable silyl ethers (11 mol %). The alkoxy-gDFC mechanophore thus provides a mechanically coupled mechanism of releasing HF for polymer remodeling pathways that complements previous thermally driven mechanisms. 

   more » « less
2. Visible-light-driven net-1,2-hydrogen atom transfer of amidyl radicals to access β-amido ketone derivatives

   https://doi.org/10.1039/D4SC04997G  

   Jiang, Yonggang; Li, Hui; Tang, Haoqin; Zhang, Qingyue; Yang, Haitao; Pan, Yu; Zou, Chenggang; Zhang, Hongbin; Walsh, Patrick J; Yang, Xiaodong (January 2025, Chemical Science)

   Visible-light-driven N-centered radicals lead to C-centered α-amino radicals through rare net-1,2-HAT processes, with trapping by silyl enol ethers to access β-amido ketone derivatives. 

   more » « less
3. Experimental nitrogen fertilisation globally accelerates, then slows decomposition of leaf litter

   https://doi.org/10.1111/ele.13700  

   Gill, Allison L.; Schilling, Jonathan; Hobbie, Sarah E.; Liu, ed., Lingli (February 2021, Ecology Letters)

   Abstract Plant litter decomposition is a central process in the carbon (C) cycle and sensitive to ongoing anthropogenic nitrogen (N) fertilisation. Previous syntheses evaluating the effect of N fertilisation on litter decomposition relied largely on models that define a constant rate of mass loss throughout decomposition, which may mask hypothesised shifts in the effect of N fertilisation on litter decomposition dynamics. In this meta‐analysis, we compared the performance of four empirical decomposition models and showed that N fertilisation consistently accelerates early‐stage but slows late‐stage decomposition when the model structure allows for flexibility in decomposition rates through time. Within a particular substrate, early‐stage N‐stimulation of decomposition was associated with reduced rates of late‐stage decay. Because the products of early‐ vs. late‐stage decomposition are stabilised in soils through distinct chemical and physical mechanisms, N‐induced changes in the litter decomposition process may influence the formation and cycling of soil C, the largest terrestrial C pool. 

   more » « less
4. Modular Approach to Bio-Based Poly(enol ether)s with Tunable Thermal Properties and Degradability

   https://doi.org/10.1021/acsapm.3c03196  

   Ibrahim, Tarek; Sun, Hao (February 2024, ACS Applied Polymer Materials)

   Biomass-derived polymer materials are emerging as sustainable and low-carbon footprint alternatives to the current petroleum-based commodity plastics. In the past decade, the ring-opening metathesis polymerization (ROMP) technique has been widely used for the polymerization of cyclic olefin monomers derived from biorenewable resources, giving rise to a diverse set of biobased polymer materials. However, most synthetic biobased polymers made by ROMP are nondegradable because of their all-carbon backbones. Herein, we present a modular synthetic strategy to acid-degradable poly(enol ether)s via ring-opening metathesis copolymerization of biorenewable oxanorbornenes and 3,4-dihydropyran (DHP). 1H NMR analysis reveals that the percentage of DHP units in the resulting copolymers gradually increases as the feed ratio of DHP to oxanorbornene increases. The composition of the copolymers plays a pivotal role in governing their thermal properties. Thermogravimetric analysis shows that an increasing percentage of DHP results in a decrease in the decomposition temperatures, suggesting that the incorporation of enol ether groups in the polymer backbone reduces the thermal stability of the copolymers. Moreover, a wide range of glass transition temperatures (16–165 °C) can be achieved by tuning the copolymer composition and the oxanorbornene structure. Critically, all of the poly(enol ether)s developed in this study are degradable under mildly acidic conditions. A higher incorporation of DHP in the copolymer leads to enhanced degradability, as evidenced by smaller final degradation products. Altogether, this study provides a facile approach for synthesizing biorenewable and degradable polymer materials with highly tunable thermal properties desired for their potential industrial applications. 

   more » « less
5. Heterolytic Cleavage of L _n Pd–SiR ₃ ⁺ Bonds Enable the Ring-Opening C–C Functionalization of Nonstrained Ethers

   https://doi.org/10.1021/jacs.5c12528  

   Owen, Bradley A; Basemann, Kevin; Hearne, William A; Gagné, Michel R (August 2025, Journal of the American Chemical Society)

   Silyl palladium cations (R3P)2Pd–SiR3+ catalyze the ring opening, C–C bond forming, and functionalization of 5- and 6-membered cyclic allyl ethers with O-silyl nucleophiles. Conditions for high regio-control are achieved by adjustments in the phosphine electronics, with the identity of the 2-substituent also influencing the functionalization location in unsymmetrical furans. Allyl alcohols are obtained with a regio-preference for terminal addition with unsubstituted ethers with E-products being obtained with XantPhos and Z- with (4-CF3–Ar)3 ligation. Styrenes dominate with phenyl-substituted dihydrofurans, and for 2-alkyl-substituted, secondary alcohols result from an allyl migration pathway. Mechanistic studies demonstrate the feasibility of Pd–Si+ bonds to facilitate C–O activation to yield π-allyl intermediates, and for one substrate class to also sequence π-allyl migration prior to nucleophilic addition. DFT calculations demonstrated the viability of silylium-activated ether as a competent ligand for Pd(0). 

   more » « less