Synthesis and Properties of 1,6-Difunctionalized Cyclodeca-3,8-diynes

Abstract

The reaction of tert-butyl acetate (6) with 1,4-dibromobut-2-yne (1) in the presence of LDA yielded 1,6-di(tert-butyl)cyclodeca-3,8-diyne-1,6-dicarboxylate (8). The 1,6-di(tert-butyl) groups of 8 were transferred to bis(hydroxymethyl) (5), bis(bromomethyl) (13), bis(cyanomethyl) (14), dicarbaldehyde (15) and bis(methoxyvinyl) (16) groups. In case of 13 the two diastereomers [cis(a,e), trans(a,a)] were separated. From 13(a,e) and 14(a,a) we were able to obtain detailed structural parameters by means of X-ray crystallography. By means of temperature dependent NMR spectroscopy of 14(a,a) we estimated the activation energy for the chair-boat conversion to be 10.5 kcal/mol.

Key words

aldehydes - alkynes - condensations - cyclizations - esters

References

• 1a Ziegler K. In Methoden der Organischen Chemie, Houben-Weyl   Vol. IV/2:  Müller E. Georg Thieme Verlag; Stuttgart: 1955.  p.729-822  
• 1b Illuminati G. Mandolini L. Acc. Chem. Res.  1981,  14:  95 
• 2a Dale J. Angew. Chem., Int. Ed. Engl.  1966,  5:  1000 ; Angew. Chem. 1966, 78, 1070
• 2b Dietrich B. Viout P. Lehn J.-M. In Macrocyclic Chemistry   VCH; Weinheim: 1993. 
• 3a Gleiter R. Merger R. In Modern Acetylene Chemistry   Stang PJ. Diederich F. VCH; Weinheim: 1995.  p.285-319  
• 3b Gleiter R. Angew. Chem., Int. Ed. Engl.  1992,  31:  27 ; Angew. Chem. 1992, 104, 29
• 4 Gleiter R. Merger R. Nuber B. J. Am. Chem. Soc.  1992,  114:  8921 
• 5 Etournaud A. Wyler H. Helv. Chim. Acta  1973,  56:  625 
• 6 Brillon D. Deslongchams P. Tetrahedron Lett.  1986,  27:  1131 
• 8 Ramming M. Diplomarbeit   Universität Heidelberg; Germany: 1992. 
• 9a Cregge RJ. Herrmann J.-L. Lee CS. Richman JE. Schlessinger RH. Tetrahedron Lett.  1973,  15:  2425 
• 9b Petragnani N. Yonashiro M. Synthesis  1982,  521 
• 10 Chandrasekaran S. Kluge AF. Edwards JA. J. Org. Chem.  1977,  42:  3972 
• 11 Hassner A. Alexanian V. Tetrahedron Lett.  1978,  20:  4475 
• 12 Noller CR. Adams R. J. Am. Chem. Soc.  1926,  48:  1080 
• 13 Hayashi H. Nakanishi K. Brandon C. Marmur J. J. Am. Chem. Soc.  1973,  95:  8749 
• 14 Roedig A. In Methoden der Organischen Chemie, Houben-Weyl   Vol. V/4:  Müller E. Georg Thieme Verlag; Stuttgart: 1960.  p.595-605  
• 15a Omura K. Swern D. Tetrahedron  1978,  34:  1651 
• 15b Manusco AJ. Swern D. Synthesis  1981,  165 
• 16 Gleiter R. Karcher M. Jahn R. Irngartinger H. Chem. Ber.  1988,  121:  735 
• 17 Kessler H. Angew. Chem., Int. Ed. Engl.  1970,  9:  219 ; Angew. Chem. 1970, 82, 237
• 18 Ritter J. Gleiter R. Irngartinger H. Oeser T. J. Am. Chem. Soc.  1997,  119:  10599 

7

Ramming, M. unpublished results.

19

Data sets were collected on a Enraf-Nonius CAD4 [13(a,e)] and a Bruker Smart CCD diffractometer.