Reactions of secondary propargylamines with heteroallenes for the synthesis of diverse heterocycles

Abstract

This focused review aims to summarize recent developments in the processes involving additions of secondary propargylamines to various heteroallenes and subsequent transition metal-catalyzed or electrophile-mediated cyclizations. The utility of this convenient and tunable strategy spans from the carbon dioxide fixation and target-oriented synthesis of complex natural and biologically active products to the generation of extended synthetic libraries of diverse oxygen-, nitrogen- and sulfur-containing heterocycles. For comparative purposes, the analogous transformations of propargylic alcohols are also highlighted in this account.

Scope and advances in the catalytic propargylic substitution reaction

“…Transition metal/Brønsted acid catalyzed intramolecular cycloisomerization of propargylic sub-unit offers a new dimension for the synthesis of extremely useful building blocks for organic synthesis as highlighted in Scheme 7 and Scheme 8. [33][34][35][36][37][38][39][40] The nature of the catalysts and the structure of propargyl derivatives have great inuences on the cyclization modes. These cyclization reactions, due to their ability to rapidly assemble into structurally complex molecules and good functional group compatibility, have emerged as an outstanding method for the synthesis of N-containing heterocycles.…”

Synthesis of Oxazolidin‐2‐ones from Unsaturated Amines with CO2 by Using Homogeneous Catalysis

“…Many different types of catalytic system, such as transition metal catalysis, organocatalysis, and photocatalysis, have been used with amine substrates that contain various unsaturated bonds to realize such reactions. However, to the best of our knowledge, there have been few reviews of the elegant synthesis of oxazolidin‐2‐ones from unsaturated amines with CO 2 . Therefore, this Focus Review will highlight recent progress on the synthesis of oxazolidin‐2‐ones from three kinds of unsaturated amine: amines that contain alkynes, alkenes, and allenes.…”

Pivotal Role of the Basic Character of Organic and Salt Catalysts in C−N Bond Forming Reactions of Amines with CO2

“…Reactions of aziridines, [99][100][101] propargylic amines,a llylic amines and 1,2-aminoalcohols with CO 2 yield oxazolidinones and their derivatives (Scheme 12) [102][103][104][105][106][107] and six-membered oxazin-2-ons from allenic amines [108,109] or 2-ethynylaniline (Scheme 13). [110] 2-Ethynylanilines are isostructural with 2- Figure 14.…”