Rules for predicting anionic SN2 displacement viability in furanose and furanoside sulfonates are presented.
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Recent advances of 5- radical cyclization: promoting strategies and applications.
Chem Commun (Camb)
September 2024
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Science, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang 321004, China.
5- radical cyclization has long been recognized as one of the most straightforward ways for the construction of densely functionalized five-membered rings. Nevertheless, according to Baldwin's rules, the 5- radical cyclization is kinetically disfavored due to stereoelectronic effects and thus usually proceeds a slow rate, which renders its application a challenging task. In recent years, with the emergence of efficient radical generation methods and effective cyclization strategies, 5- radical cyclization has been successfully accelerated to a synthetically useful rate and has been utilized in the access of diverse five-membered carbo- and heterocyclic compounds.
View Article and Find Full Text PDFDissecting the Conformational Stability of a Glycan Hairpin.
J Am Chem Soc
March 2024
Department of Biomolecular Systems, Max Planck Institute of Colloids and Interfaces, Am Mühlenberg 1, Potsdam 14476, Germany.
Systematic structural studies of model oligopeptides revealed important aspects of protein folding and offered design principles to access non-natural materials. In the same way, the rules that regulate glycan folding could be established by studying synthetic oligosaccharide models. However, their analysis is often limited due to the synthetic and analytical complexity.
View Article and Find Full Text PDFIn small molecule organic chemistry, the heuristic insight into ring-forming processes that was enabled by Baldwin's rules some 50 years ago proved a step-change in the role of mechanistically guided synthesis. It created a lens upon and marker of fundamental stereoelectronic and conformation-guided chemical processes. However, despite the widespread role of stereoelectronics and conformational control in Biology, no equivalent coherent exploitation of trapped, ring-forming processes yet exists in biomolecules.
View Article and Find Full Text PDF6-Endo-dig versus 5-exo-dig: Exploring Radical Cyclization Preference with First-, Second-, and Third-row Linkers using High-level Quantum Chemical Methods.
Chemphyschem
September 2023
School of Science and Technology, University of New England, Armidale, NSW 2351, Australia.
As an expansion upon Baldwin rules, the cyclization reactions of hex-5-yn-1-yl radical systems with different first-, second-, and third-row linkers are explored at the CCSD(T) level via means of the SMD(benzene)-G4(MP2) thermochemical protocol. Unlike C, O, and N linkers, systems with B, Si, P, S, Ge, As, and Se linkers are shown to favor 6-endo-dig cyclization. This offers fundamental insights into the rational synthetic design of cyclic compounds.
View Article and Find Full Text PDFDesigning an Apparently Orbital-Symmetry-Forbidden [3s,5s]-Sigmatropic Shift through Transition-State Complexation and Stereoelectronic Effects.
Angew Chem Int Ed Engl
April 2023
Department of Chemistry, University of California, Davis, One Shields Avenue, Davis, CA-95616, USA.
The [3s,5s]-sigmatropic shift is an example of an orbital-symmetry forbidden pericyclic reaction that is outcompeted by the allowed [3s,3s]-sigmatropic shift. Density functional theory calculations are used to show that Pd -complexed systems with strategically placed substituents engaging in key stereoelectronic effects can select for the [3s,5s] process, thereby outcompeting both orbital-symmetry-allowed [3s,3s]- and [3s,5a]-shifts.
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