An efficient and stereoselective approach to 14-membered hexaaza macrocycles using novel semicarbazone-based amidoalkylation reagents. Issue 51 (21st December 2016)

• Record Type: Journal Article
• Authors: Fesenko, Anastasia A.; Yankov, Alexander N.; Shutalev, Anatoly D.
• Is Part Of: Tetrahedron letters. Volume 57:Issue 51(2016)
• Page Start: 5784
• Page End: 5787
• Publication Date: 2016-12-21
• Subjects: RZLVGGROKOHKBT-XQNSMLJCSA-N -- FYBRSXQFLQCKEK-PCLIKHOPSA-N -- XBSJUPHGIPBNIE-AJBULDERSA-N -- DSKZKXAVXLKTCB-PCLIKHOPSA-N -- CYVGGOQXKUOEKI-FYJGNVAPSA-N -- GMYKHUJPVFCIBZ-YDZHTSKRSA-N -- NPUYPEROIBODNE-STBIYBPSSA-N -- BWAWNLGQQICRTD-YDZHTSKRSA-N -- LSILVWILUDRGCT-CPNJWEJPSA-N -- ZJIQBVHMXCKWEF-FYJGNVAPSA-N -- WZLIWNPODCPEGP-WPWMEQJKSA-N -- PLCWEVVIGFVBNE-FYJGNVAPSA-N -- MEUNWPREWOMOEY-CXUHLZMHSA-N -- UFRUXCJMYHRLCH-OVCLIPMQSA-N -- YSKNRHUUURGOBW-VXLYETTFSA-N -- XTUQVHXMRVTXCQ-STHOXOPSSA-N -- GFTAOOBRGPDIKA-LUPKMHDTSA-N -- MWRNVRYRXBFRBB-FYQGUJEDSA-N -- WFKLFTGKODHUMC-ANGVJMTBSA-N -- IPNUUBFOCNNSHG-UJOYTAFJSA-N -- CZISUPBEWROIHZ-RYQLWAFASA-N -- WXAJODSWXCLNTC-XUIWWLCJSA-N -- QTODEZVQHUKSMF-ZXHXELASSA-N -- MNQBFIUABIISIR-DPCVLPDWSA-N; Semicarbazones -- Semicarbazides -- Hydrazones -- Amidoalkylation -- retro-Claisen reaction -- Azamacrocycles; Chemistry, Organic -- Periodicals; 547.005
• DOI: 10.1016/j.tetlet.2016.11.041
• Languages: English
• ISSNs: 0040-4039

Abstract

Graphical abstract: Highlights: Novel amidoalkylation reagents, 4-[(aryl)(tosyl)methyl]semicarbazones, were prepared. Synthesis of hydrazones of 4-(3-oxobutyl)semicarbazides was developed. Synthesis of hydrazones of 4-(3-oxobutyl)semicarbazones was developed. The prepared hydrazones were converted into 14-membered cyclic bis-semicarbazones. Plausible pathway and stereochemistry of the macrocyclization were discussed. Abstract: An efficient synthesis of hydrazones of 4-(3-oxobutyl)semicarbazides and 4-(3-oxobutyl)semicarbazones using novel semicarbazone-based amidoalkylation reagents, 1-arylidene-4-[(aryl)(tosyl)methyl]semicarbazides, has been developed. The synthesis involved reaction of the latter with the Na-enolate of acetylacetone, followed by a base-promoted retro-Claisen reaction and treatment of the obtained 4-(3-oxobutyl)semicarbazones with hydrazine or methylhydrazine. The prepared hydrazones were converted stereoselectively into 14-membered cyclic bis-semicarbazones under acidic conditions. Especially high selectivity ( trans / cis ⩾ 97:3) was observed upon the macrocyclization of 4-(3-oxobutyl)semicarbazone hydrazones. A plausible reaction pathway and the stereochemistry of this cyclization were discussed.