Gold‐Catalyzed Sequential Cycloisomerization of 1,3,9‐Ene‐allene‐ynes to Fused Spirocarbocycles

• Published in: European journal of organic chemistry Vol. 2020; no. 32; pp. 5227 - 5233
• Main Authors: Chen, Xianxiao, Ling, Xiangxiang, An, Di, Rao, Weidong
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 31.08.2020; Wiley Subscription Services, Inc
• Subjects: Allene; Chemistry; Chemistry, Organic; Cycloaddition; Ene‐allene‐ynes; Fused carbocycles; Gold; Isomerization; Naphthalene; Physical Sciences; Science & Technology; Sequential cycloisomerization; Synthetic methods; Gold; NATURAL-PRODUCTS; Ene-allene-ynes; 2+2+2 CYCLOADDITION; RING-SYSTEM; REARRANGEMENTS; Fused carbocycles; Sequential cycloisomerization; HETEROCYCLES; ARYLALKYNES; ALLENE-ENE-YNES; CONSTRUCTION; Synthetic methods; LIGAND; CYCLIZATION
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.202000851

An efficient synthetic method to prepare architecturally challenging spiro tetrahydro‐3H‐dicyclopenta[a,b]naphthalene derivatives from Au(I)‐catalyzed intramolecular sequential cycloisomerization of linear 1,3,9‐ene‐allene‐ynes is described. The proposed cycloisomerization pathway involves an initial gold‐catalyzed 1,3‐ene‐allene cycloisomerization, followed by a formal [4+2] cycloaddition to give fused spirocarbocyclic products containing a quaternary centre. An efficient Au(I)‐catalyzed intramolecular sequential cycloisomerization of linear 1,3,9‐ene‐allene‐ynes to prepare architecturally challenging spiro tetrahydro‐3H‐dicyclopenta[a,b]naphthalene derivatives is reported. The proposed mechanism involves an initial gold‐catalyzed 1,3‐ene‐allene cycloisomerization, followed by a formal [4+2] cycloaddition to give the fused spirocarbocyclic products containing a quaternary centre in excellent efficiency.