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Acyclic α-tertiary ethers represent a highly prevalent functionality, common to high-value bioactive molecules, such as pharmaceuticals and natural products, and feature as crucial synthetic handles in their construction. As such their synthesis has become an ever-more important goal in synthetic chemistry as the drawbacks of traditional strong base- and acid-mediated etherifications have become more limiting. In recent years, the generation of highly reactive intermediates redox approaches has facilitated the synthesis of highly sterically-encumbered ethers and accordingly these strategies have been widely applied in α-tertiary ether synthesis. This review summarises and appraises the state-of-the-art in the application of redox strategies enabling acyclic α-tertiary ether synthesis.
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http://dx.doi.org/10.1039/d1cs00669j | DOI Listing |
J Am Chem Soc
September 2025
Kekulé Institute for Organic Chemistry and Biochemistry, University of Bonn,Gerhard-Domagk-Straße 1,Bonn 53121,Germany.
Terpene synthases produce a remarkable structural diversity from acyclic precursors through complex carbocation cascades. Here, we report the crystal structure of the bacterial sesterterpene synthase StvirS bound to geranylfarnesyl thiopyrophosphate (GFSPP), revealing a preorganized active site that enforces a defined folding of the C25 backbone. Guided by this structure, active-site engineering at 11 positions yielded 23 enzyme variants and 13 new sesterterpenes.
View Article and Find Full Text PDFCien Saude Colet
August 2025
Departamento de Medicina Social, Faculdade de Medicina de Ribeirão Preto, Universidade de São Paulo. Ribeirão Preto SP Brasil.
The present study aimed to investigate the relationship between screen time and the frequency of consumption of ultra-processed foods (UPF) in overweight pregnant women. This was a cross-sectional study that used baseline data from a randomized clinical trial conducted in the Primary Health Care (PHC) network of a Brazilian municipality between 2018 and 2021. Data from the Food Consumption Markers form were used.
View Article and Find Full Text PDFChemistry
September 2025
ICGM, Univ, Montpellier, ENSCM, CNRS, Montpellier, France.
A novel Ru-catalyzed asymmetric transfer hydrogenation (ATH) strategy has been developed for the efficient synthesis of valuable chiral α-aminophosphonates from readily available α-iminophosphonates. This method enables the conversion of both acyclic and cyclic substrates in high yields (up to 97%) and excellent enantioselectivities (up to >99:1), providing a practical entry to phosphorus-containing chiral amines. Notably, this is the first reported application of ATH to α-iminophosphonates, offering a robust and operationally convenient alternative to conventional asymmetric hydrogenation (AH) approaches.
View Article and Find Full Text PDFNat Chem
September 2025
Division of Medicinal and Process Chemistry, CSIR-Central Drug Research Institute, Lucknow, India.
[2,1]-Azaboranaphthalenes represent unique boron-nitrogen (BN) isosteres of naphthalenes, attracting interest for the development of molecules with enhanced therapeutic potency. The existing synthetic strategies are generally two-component reactions with harsh conditions. Here we report an organocatalysed three-component modular synthesis of ring-fused BN isosteres and BN-2,1-azaboranaphthalenes following ring expansion of unstrained cyclic ketones (n = 4-8) via Wolff-type rearrangement.
View Article and Find Full Text PDFBMJ Public Health
September 2025
Centre for Women's Health Research, School of Medicine and Public Health, College of Health, Medicine and Wellbeing, The University of Newcastle, Australia, Newcastle, New South Walses, Australia.
Introduction: Diarrhoea and malnutrition (stunting, wasting and underweight) are major public health problems in developing countries, including Nepal. Improved water, sanitation and hygiene (WASH) may reduce the global disease burden by as much as 10.0%.
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