One-Step Synthesis of Nitrogen-Containing Medium-Sized Rings via α-Imino Diazo Intermediates

Abstract

Eight- and 9-membered dioxazocines and dioxazonines are readily synthesized starting from N-sulfonyl-1,2,3-triazoles in a single-step procedure. A perfect regioselectivity and generally good yields (up to 92%) are obtained under dirhodium catalysis using 1,3-dioxolane and 1,3-dioxane as solvents and reagents.

Rhodium(II)‐Catalyzed Annulation of Azavinyl Carbenes Through Ring‐Expansion of 1,3,5‐Trioxane: Rapid Access to Nine‐Membered 1,3,5,7‐Trioxazonines

“…Apparently, the use of 1‐alkylsulfonyl‐triazoles as carbene precursors was crucial in the reaction with compound 1 . In contrast, 1‐arylsulfonyl triazoles have been reported to give the best results with 1,3‐dioxolane or 1,2‐dioxane in the presence of [Rh 2 (OAc) 4 ] as a catalyst in toluene at 100 °C . It is important to note that this reaction is orthogonal to the previously reported procedures.…”

“…The catalytic decomposition of N ‐sulfonyl triazoles in the presence of cyclic ethers was first observed by the groups of Fokin and Gevorgyan (Scheme b) . While this work was in progress, Lacour and co‐workers reported related reactions with cyclic acetals, such as 1,3‐dioxolane and 1,3‐dioxane, to give eight‐ and nine‐membered dioxazocines and dioxazonines, respectively (Scheme b) …”

“…[15] While this work was in progress, Lacour and co-workersr eported relatedr eactions with cyclic acetals,s uch as 1,3-dioxolane and 1,3-dioxane, to give eight-and nine-membered dioxazocines and dioxazonines, respectively (Scheme1b). [16]…”

Recent Advances in the Synthesis of Heterocycles and Related Substances Based on α‐Imino Rhodium Carbene Complexes Derived from N‐Sulfonyl‐1,2,3‐triazoles

“…[35] The reaction scope wasb road as various triazoles 1 could be used in this reaction. [35] The reaction scope wasb road as various triazoles 1 could be used in this reaction.…”

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

“…1036) [1110]. Sulfonated triazoles couple with five-and sixmembered ring cyclic acetals in the presence of a rhodium catalyst to afford eight-or nine-membered rings via rhodium carbene-derived ylide intermediates [1111]. A net C=O metathesis process was observed in the rhodium-catalyzed reaction of sulfonated triazoles (e.g.…”