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Unified, Biosynthesis-Inspired, Completely Stereocontrolled Total Synthesis of All Highest-Order [n + 1] Oligocyclotryptamine Alkaloids.
J Am Chem Soc
August 2024
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States.
We describe the unified enantioselective total synthesis of the polycyclotryptamine natural products (+)-quadrigemine H, (+)-isopsychotridine C, (+)-oleoidine, and (+)-caledonine. Inspired by our hypothesis for the biogenesis of these alkaloids via an iterative concatenative addition of homochiral cyclotryptamines to a -chimonanthine headcap, we leverage the modular, diazene-directed assembly of stereodefined cyclotryptamines to introduce successive C3a-C7' quaternary stereocenters on a heterodimeric -chimonanthine surrogate with full stereochemical control at each quaternary linkage. We developed a new strategy for iterative aryl-alkyl diazene synthesis using increasingly complex oligomeric hydrazide nucleophiles and a bifunctional cyclotryptamine bearing a C3a leaving group and a pendant C7 pronucleophile.
View Article and Find Full Text PDFSynthesis and Characterization of Bridging-Diazene Diiron Half-Sandwich Complexes: The Role of Sulfur Hydrogen Bonding.
Inorg Chem
July 2024
School of Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China.
We report two bridging-diazene diiron complexes [Cp*Fe(8-quinolinethiolate)](μ-NH) () and [Cp*Fe(1,2-CyPCHS)](μ-NH) (), synthesized by the reaction of hydrazine with the corresponding thiolate-based iron half-sandwich complex, [Cp*Fe(8-quinolinethiolate)] () and Cp*Fe(1,2-CyPCHS) (). Crystallographic analysis reveals that the thiolate sites in and can engage in N-H···S hydrogen bonding with the diazene protons. is thermally stable in both solid and solution states, allowing for one-electron oxidation to afford a cationic diazene radical complex [] at room temperature.
View Article and Find Full Text PDFFine Tuning between Radical versus Nonradical States of Azoheteroarenes on Selective Osmium Platforms.
Inorg Chem
July 2024
Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400076, India.
The article highlights the cooperative impact of azoheteroarenes [abbt: 2,2'-azobis(benzothiazole), L1-L3; bmpd: ()-1,2-bis(1-methyl-1-pyrazole-3-yl) diazene, L4] and coligands [bpy: 2,2'-bipyridine; pap: 2-phenylazopyridine] in tuning radical (N-N) versus nonradical (N═N) states of L on selective Os-platforms in structurally/spectroscopically characterized monomeric []ClO-[]ClO and [](ClO)-[](ClO)/[](ClO)-[](ClO), respectively. The preferred -configuration of L in the complexes prevented obtaining ligand bridged dimeric species. It revealed that {Os(bpy)} facilitated the stabilization of both nonradical ([](ClO)-[](ClO)) and radical ([]ClO-[]ClO) states of L1/L2, while it delivered exclusively the radical form for L3 in []ClO.
View Article and Find Full Text PDFConstruction and Function of Thiolate-Bridged Diiron NH Nitrogenase Model Complexes.
Acc Chem Res
July 2024
State Key Laboratory of Fine Chemicals, Frontier Science Center for Smart Materials, Dalian University of Technology, Dalian 116024, P. R. China.
Article Synopsis
- * Most studies have concentrated on single molybdenum or iron sites for nitrogen activation, while the potential of bi- or multimetallic centers is understudied, despite recent biochemical models suggesting their viability.
- * This research focuses on creating thiolate-bridged diiron complexes as nitrogenase models to explore nitrogen reduction pathways, ultimately demonstrating the first complex capable of catalyzing the breakdown of hydrazine into ammonia.
Evaluating Diazene to N Interconversion at Iron-Sulfur Complexes.
Chemistry
April 2024
Department of Chemistry, Yale University, 225 Prospect Street, New Haven, CT-06511.
Biological N reduction occurs at sulfur-rich multiiron sites, and an interesting potential pathway is concerted double reduction/ protonation of bridging N through PCET. Here, we test the feasibility of using synthetic sulfur-supported diiron complexes to mimic this pathway. Oxidative proton transfer from μ-η : η-diazene (HN=NH) is the microscopic reverse of the proposed N fixation pathway, revealing the energetics of the process.
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