Intramolekulare Cycloaddition von [1,1′-Binaphthyl]-2,2′-bis(allylamin)

✍ Scribed by Yushin Nakamura; Janos Zsindely; Hans Schmid

• Publisher: John Wiley and Sons
• Year: 1977
• Tongue: German
• Weight: 453 KB
• Volume: 60
• Category: Article
• ISSN: 0018-019X
• DOI: 10.1002/hlca.19770600130

✦ Synopsis

Intramolecular cycloaddition of [1,1′‐binaphthyl]‐2,2′‐bis(allylamine)

Unlike the 1,1′‐binaphthyl‐2,2′‐bis(allylether) the corresponding [1,1′‐binaphthyl]‐2,2′‐bis(allylamine) (1) upon heating to 230° in mesitylene undergoes thermal decomposition only. However, when 1 is heated in a mixture of 2‐methylaminoethanol and water, besides 3 the policyclic ketones 4 and 5 are formed in isolated yields of 28 and 10%, respectively (Scheme 1). Intermediates are the imines corresponding to 4 and 5 which are hydrolysed under the reaction conditions rather than decomposed. The imines are formed by a intramolecular Diels‐Alder reaction, in which the double bond of one N‐allylgroup reacts with the naphthalene ring of the second half of the molecule.

The policyclic ketones 4 and 5 are characterized as acetates 6 and 7, respectively, and as the acetylated reduced products 11, and 12 and 13, respectively. The constitutions of all compounds are derived from spectroscopic data, chiefly from the ^1^H‐NMR. spectra.