Direct and Stereospecific Synthesis of N‐H and N‐Alkyl Aziridines from Unactivated Olefins Using Hydroxylamine‐O‐Sulfonic Acids

Abstract

Graphical abstract Herein we report a Rh(II)-catalyzed direct and stereospecific N–H- and N–alkyl aziridination of olefins that uses hydroxylamine-O-sulfonic acids as inexpensive, readily available and nitro group-free aminating reagents. Unactivated olefins, featuring a wide range of functional groups, are converted to the corresponding N–H or N–alkyl aziridines in good to excellent yields. This operationally simple, scalable transformation proceeds efficiently at ambient temperature and is tolerant towards oxygen and trace moisture.

Direct Formic Acid MediatedZ‐Selective Reductive Coupling of Dienes and Aldehydes

“…[14] Thestereochemically defined Z-allylic alcohols generated by formic acid mediated reductive coupling are useful building blocks for more complex fragments ( Figure 6). Straight-forward access to 2,5-dihydrofurans (7), [15] epoxide, [16] and aziridine [17] stereotetrads (8,9), tertiary alcohols (10), [18] and tetrasubstituted tetrahydrofurans (11) [12] is possible by the high-yielding stereoselective functionalization of 2a by standard synthetic protocols.…”

Rh‐Catalyzed Aminative Dearomatization of Naphthols with Hydroxylamine‐O‐Sulfonic Acid (HOSA)

“…Therefore, it is in great demand to find an alternative aminating reagent to overcome the aforementioned limitations. Notably, Kürti and co‐workers recently reported Rh 2 (esp) 2 catalyzed aziridination reaction of unactivated alkenes with hydroxylamine‐ O ‐sulfonic acid (HOSA) as a suitable aminating reagent . Inspired by this work, we report here a Rh‐catalyzed aminative dearomatization reaction of naphthols with HOSA (Scheme b).…”

Dirhodium Coordination Polymers for Asymmetric Cyclopropanation of Diazooxindoles with Olefins: Synthesis and Spectroscopic Analysis

“…[13][14][15][16][17][18][19][20][21][22][23][24][25] Recently, they have also emerged as catalysts in CÀ H amination and olefin aziridination. [12,[26][27][28][29][30][31][32][33][34][35][36][37] This variety of reactions makes chiral dirhodium catalysts especially attractive for synthesis of pharmaceuticals or biological active substances. For example, spiro-cyclopropyloxindole compounds can be synthesized by cyclopropanation of diazooxindoles with olefins employing chiral dirhodium catalysts.…”