Reported herein is a new iron-catalyzed diastereo-selective olefin diazidation reaction which occurs at room temperature (1-5 mol % of catalysts and d.r. values of up to > 20:1). This method tolerates a broad range of both unfunctionalized and highly functionalized olefins, including those that are incompatible with existing methods. It also provides a convenient approach to vicinal primary diamines as well as other synthetically valuable nitrogen-containing building blocks which are difficult to obtain with alternative methods. Preliminary mechanistic studies suggest that the reaction may proceed through a new mechanistic pathway in which both Lewis acid activation and iron-enabled redox-catalysis are crucial for selective azido-group transfer.
A diastereoselective aminohydroxylation of olefins with a functionalized hydroxylamine is catalyzed by new iron(II) complexes. This efficient intramolecular process readily affords synthetically useful amino alcohols with excellent selectivity (dr up to > 20:1). Asymmetric catalysis with chiral iron(II) complexes and preliminary mechanistic studies reveal an iron nitrenoid is a possible intermediate that can undergo either aminohydroxylation or aziridination, and the selectivity can be controlled by careful selection of counteranion/ligand combinations.
An enantioselective intramolecular indole aminohydroxylation reaction is catalyzed by iron(II)-chiral bisoxazoline (BOX) complexes (ee up to 99%, dr > 20:1). This discovery enables expedient asymmetric synthesis of a series of biologically active 3-amino oxindoles and 3-amino indolanes.
Reported herein is an ew iron-catalyzedd iastereoselective olefin diazidation reaction whicho ccurs at room temperature (1-5 mol %o fc atalysts and d.r.values of up to > 20:1). This method tolerates ab road range of both unfunctionalized and highly functionalizedo lefins,i ncluding those that are incompatible with existing methods.I ta lso provides aconvenient approach to vicinal primary diamines as well as other synthetically valuable nitrogen-containing building blocks which are difficult to obtain with alternative methods.P reliminary mechanistic studies suggest that the reaction may proceed through an ew mechanistic pathway in which both Lewis acid activation and iron-enabled redoxcatalysis are crucial for selective azido-group transfer.
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