Copper-Catalyzed Domino Reactions for the Synthesis of Cyclic Compounds

Abstract

Copper-catalyzed domino reactions are one of the most useful strategies for the construction of various cyclic compounds. In this Synopsis, we mainly focus on the latest advances in copper-catalyzed cross-coupling or addition-initiated domino reactions in the synthesis of cyclic compounds, including double alkenylation of N- or S-nucleophiles, alkenylation or alkynlation followed by cyclization of amides or amines, addition and cyclization of heteroallenes affording heterocycles, and coupling and cyclization of 1,3-dicarbonyl compounds toward heterocycles.

Direct Access to 1,3,5-Trisubstituted 1H-1,2,4-Triazoles from N-Phenylbenzamidines via Copper-Catalyzed Diamination of Aryl Nitriles

“…The use of AgOAc or I 2 without the presence of copper catalyst resulted in none of the desired product 3aa (Table 1, entries 5, 6). When the amount of CuI was increased to 50 mol%, 3aa was formed in 56% yield; however, higher equivalents of CuI proved to be detrimental (Table 1, 7,[9][10][11][12], with the result that CuI performed best among the copper compounds tested. Of the Lewis acid additives that were evaluated (ZnI 2 , BF 3 , FeCl 3 ), ZnI 2 provided the best outcome (Table 1, entries 7, 13, 14).…”

“…Because of its low cost and low toxicity, this type of reaction is highly appealing to modern chemists. 7,8 Recently, Zhang and co-workers have raised the possibility of producing various 1,2,3-triazoles from N-tosylhydrazones and anilines. 9 Following the successful trials on 1,2,4-triazoles, Nagasawa's group has further contributed the synthesis of [1,2,3]triazolo[1,5-a]pyridines from acylpyridines.…”

DBU‐Mediated Intermolecular 5‐exo‐dig Cyclization of PropargylAlcohols and Carbon Disulfide to [1,3]‐Oxathiole‐2‐thiones

“…The 5‐ exo ‐dig cyclization is commonly encountered methodology for making regio‐specific five‐membered cyclic compounds: till date, huge number of heterocyclic compounds have been synthesized via Baldwin rule under metal catalytic conditions. However metal mediated 5‐ exo ‐dig cyclization of sulfur containing moiety is inefficient as it poisons the catalysis quickly.…”

Synthesis and steric structure of 3′,3′,5′-trimethyl-7′,7′-bis(trifluoromethyl)spiro[1,3,2-benzodioxaphosphole-2,1′-[2,6,8]trioxa[1λ5]phosphabicyclo[3.2.1]octane] and 3′,5′-dimethyl-7′,7′-bis(trifluoromethyl)spiro[1,3,2-benzodioxaphosphole-2,1′-[2,6,8]trioxa[1λ5]phosphabicyclo[3.2.1]oct[3]ene]

“…

Reactions of hexafluoroacetone with 4-(1,3,2-benzodioxaphosphol-2-yloxy)-4-methylpentan-2-one and 4-(1,3,2-benzodioxaphosphol-2-yloxy)pent-3-en-2-one afforded cage spiro phosphoranes with a phosphorus-carbon bond, 3′,3′,5′-trimethyl-7′, 7′-bis(trifluoromethyl)spiro[1,3,2-benzodioxaphosphole-2,1′-[2,6,8]-trioxa[1λ 5 ]phosphabicyclo[3.2.1]octane] and 3′,5′-dimethyl-7′,7′-bis(trifluoromethyl)spiro[1,3,2-benzodioxaphosphole-2,1′-[2,6,8]trioxa[1λ 5 ]phosphabicyclo[3.2.1]oct[3]ene], whose structure was determined by X-ray analysis.Cascade (domino) and related reactions in threecomponent systems underlie a rapidly developing synthetic approach to complex heterocyclic structures [1][2][3][4][5]. We have recently demonstrated the application of this approach to the synthesis of complex cage phosphoranes containing a phosphor-carbon bond via reaction of activated unsaturated systems (carbonyl compounds, alkynes) with P(III) derivatives having a carbonyl or imino group in the γ-or δ-position with respect to the phosphorus atom.

…”

“…Cascade (domino) and related reactions in threecomponent systems underlie a rapidly developing synthetic approach to complex heterocyclic structures [1][2][3][4][5]. We have recently demonstrated the application of this approach to the synthesis of complex cage phosphoranes containing a phosphor-carbon bond via reaction of activated unsaturated systems (carbonyl compounds, alkynes) with P(III) derivatives having a carbonyl or imino group in the γ-or δ-position with respect to the phosphorus atom.…”