Ruthenium-Catalyzed Transformations of Cyclopropylethynes [1]

Abstract

The addition of various carboxylic acids to (trans-2-ethoxycyclopropyl)ethyne (1) by catalysis with [Ru(O₂CH)(CO)₂(PPh₃)]₂ proceeds regioselectively in the Mar­kovnikov sense with ring opening of the cyclopropyl group to furnish allenylacetaldehyde acyl ethyl acetals 3 in high yields (44-96%, 11 examples). The allenylacetaldehyde derivatives undergo palladium-catalyzed Heck-type cross coupling with iodobenzene and subsequent trapping of the π-allylpalladium intermediate with primary and secondary amines to yield labile [β-(1-aminomethyl)styryl]acetaldehyde acyl ethyl acetals 12 (24-83%, 4 examples). Anti-Markovnikov addition of carboxylic acids to the triple bond in (trans-2-ethoxycyclopropyl)ethyne (1) without ring opening can be brought about under [Ru(CH₂CMeCH₂)₂(dppb)] catalysis to give 2-(trans-2-ethoxycyclopropyl)ethenyl esters 13 (69-92%, 3 examples). (1-Hydroxycyclopropyl)ethyn­e (14), under catalysis by [Ru(O₂CH)(CO)₂(PPh₃)]₂, reacts with carboxylic acids to yield 1-acetylcyclopropyl esters 15 (49-74%, 4 examples) by Markov­nikov-sense addition and intramolecular transesterification. Anti-Markovnikov- and Markovnikov-sense addition of carboxylic acids to unsubstituted cyclopropylethyne can both be achieved regioselectively under catalysis with [Ru(CH₂CMeCH₂)₂(dppb)] and [Ru(O₂CH)(CO)₂(PPh₃)]₂ to furnish 2-cyclopropylethenyl esters 23 (68-98%, 6 examples) and 1-cyclopropylethenyl esters 24 (66-97%, 5 examples), respectively.

Key words

acetylenes - cyclopropanes - allenes - ruthenium catalysis - palladium catalysis

References

• 1xFor AdM, this is to count as Part 145 in the series ‘Cyclopropyl Building Blocks for Organic Synthesis’.
• 1x For Part 144, see: Nakamura I. Nagata R. Nemoto T. Terada M. Yamamoto Y. Späth T. de Meijere A. Eur. J. Org. Chem.  2007,  4479 
• 1x For Part 143, see: Yucel B. Valentić N. Noltemeyer M. de Meijere A. Eur. J. Org. Chem.  2007,  4081 
• 1 Acetylene Chemistry   Diederich F. Stang PJ. Tikwinski RR. Wiley-VCH; Weinheim: 2004. 
• 2a Naota T. Takaya H. Murahashi SI. Chem. Rev.  1998,  98:  2599 
• 2b Ruthenium Catalysts and Fine Chemistry, In Topics in Organometallic Chemistry, Vol. 11   Bruneau C. Dixneuf P. H. Springer; Heidelberg: 2004. 
• 3a Bruneau C. Dixneuf PH. Acc. Chem. Res.  1999,  32:  311 
• 3b Bruneau C. Dixneuf PH. Angew. Chem. Int. Ed.  2006,  45:  2176 
• 3c Bruneau C. Top. Organomet. Chem.  2004,  11:  125-153  
• 4a Suzuki N. Kondo T. Mitsudo T. Organometallics  1998,  17:  766 
• 4b Morimoto T. Chatani N. Fukumoto Y. Murai S. J. Org. Chem.  1997,  62:  3762 
• 4c Nishida M. Adachi N. Onozuka K. Matsumura H. Mori M. J. Org. Chem.  1998,  63:  9158 
• 4d Trost BM. Toste FD. J. Am. Chem. Soc.  1999,  121:  9728 
• 4e Dérien S. Dixneuf PH. J. Organomet. Chem.  2004,  689:  1382 
• 5 Rotem M. Shvo Y. Organometallics  1983,  2:  1689 
• 6a Mori M. Sakakibara N. Kinoshita A. J. Org. Chem.  1998,  63:  6082 
• 6b Zuercher WJ. Scholl M. Grubbs RH. J. Org. Chem.  1998,  63:  4291 
• 6c Picquet M. Bruneau C. Dixneuf PH. Chem. Commun.  1998,  2249 
• 6d Semeril D. Bruneau C. Dixneuf PH. Adv. Synth. Catal.  2002,  344:  585 
• 7 Chatani N. Morimoto T. Muto T. Murai S. J. Am. Chem. Soc.  1994,  116:  6049 
• 8a Liese T. de Meijere A. Angew. Chem., Int. Ed. Engl.  1982,  21:  65 ; Angew. Chem. 1982, 94, 65, Angew. Chem. Suppl. 1982, 34
• 8b Liese T. de Meijere A. Chem. Ber.  1986,  119:  2995 
• 8c Keyaniyan S. Apel M. Richmond JP. de Meijere A. Angew. Chem., Int. Ed. Engl.  1985,  24:  770 ; Angew. Chem. 1985, 97, 763
• 8d Bengtson G. Keyaniyan S. de Meijere A. Chem. Ber.  1986,  119:  3607 
• 8e de Meijere A. Schulz T.-J. Kostikov RR. Graupner F. Murr T. Bielfeldt T. Synthesis  1991,  547 
• 8f Militzer HC. Schömenauer S. Otte C. Puls C. Hain J. Bräse S. de Meijere A. Synthesis  1993,  998 
• 8g Bräse S. Schömenauer S. McGaffin G. Stolle A. de Meijere A. Chem. Eur. J.  1996,  2:  545 
• 8h Flynn BL. de Meijere A. J. Org. Chem.  1999,  64:  400 
• 9 Salaün JRY. Top. Curr. Chem.  1988,  144:  1-71  
• 10 Iwasawa N. Narasaka K. Top. Curr. Chem.  2000,  207:  69-88  ; and references cited therein
• 11a Bruneau C. Neveux M. Kabouche Z. Dixneuf PH. Synlett  1991,  755 
• 11b Bruneau C. Dixneuf PH. Chem. Commun.  1997,  507 
• 11c Doucet H. Derrien N. Kabouche Z. Bruneau C. Dixneuf PH. J. Organomet. Chem.  1997,  551:  151 
• 11d Neveux M. Seiller B. Hagedorn F. Bruneau C. Dixneuf PH. J. Organomet. Chem.  1993,  451:  133 
• 11e Seiller B. Heins D. Bruneau C. Dixneuf PH. Tetrahedron  1995,  51:  10901 
• 11f Doucet H. Höfer J. Bruneau C. Dixneuf PH. J. Chem. Soc., Chem. Commun.  1993,  850 
• 11g Doucet H. Martin-Vaca B. Bruneau C. Dixneuf PH. J. Org. Chem.  1995,  60:  7247 
• 11h Doucet H. Höfer J. Derrien N. Bruneau C. Dixneuf PH. Bull. Soc. Chim. Fr.  1996,  133:  939 
• 11i Picquet M. Bruneau C. Dixneuf PH. Chem. Commun.  1997,  1201 
• 11j Le Paih J. Dérien S. Dixneuf PH. Chem. Commun.  1999,  1437 
• 11k Le Paih J. Monnier F. Dérien S. Dixneuf PH. Clot E. Eisenstein O. J. Am. Chem. Soc.  2003,  125:  11964 
• 13 Emme I. Bruneau C. de Meijere A. Dixneuf PH. Synlett  2000,  1315 
• 14 Possibly, the cyano group participates in the ruthenium-catalyzed reaction, see ref. 3a and original publications cited therein
• 15a Dalla V. Pale P. Tetrahedron Lett.  1994,  35:  3525 
• 15b Pale P. Cuche J. Tetrahedron Lett.  1987,  28:  6447 
• 15c Jong TT. Williard PG. Porwell JP. J. Org. Chem.  1984,  49:  735 
• 15d Yamamoto M. J. Chem. Soc., Perkin Trans. 1  1981,  582 
• 15e Jellal A. Grimaldi J. Santelli M. Tetrahedron Lett.  1984,  25:  3179 
• 15f Yamamoto M. J. Chem. Soc., Chem. Commun.  1978,  649 
• 15g Kraft GA. Katzenellenbogen JA. J. Am. Chem. Soc.  1981,  103:  5459 
• 15h Spencer RW. Tam TF. Thomas E. Robinson VJ. Krantz A. J. Am. Chem. Soc.  1986,  108:  5589 
• 15i Castner J. Pascual J. J. Chem. Soc.  1958,  3962 
• 15j Pale P. Chuche J. Tetrahedron Lett.  1987,  28:  6447 
• 16a Zimmer R. Dinesh CU. Nandanan E. Khan FA. Chem. Rev.  2000,  100:  3067 
• 16b Smadja W. Chem. Rev.  1983,  83:  263 
• 16c Alkynes, Di- and Polyynes, Allenes, Cumulenes, In Houben-Weyl   4th ed., Vol. 5/2a:  Müller E. Thieme; Stuttgart: 1977. 
• 17a Shimizu I. Tsuji J. Chem. Lett.  1984,  233 
• 17b Grigg R. Brown S. Sridharan V. Uttley MD. Tetrahedron Lett.  1998,  39:  3247 
• 17c Bando T. Harayama H. Fukazawa Y. Shiro M. Fugami K. Tanaka S. Tamura Y. J. Org. Chem.  1994,  59:  1465 
• 17d Ma S. Negishi E.-I. J. Am. Chem. Soc.  1995,  117:  6345 
• 17e Ahmar M. Cazes B. Gore J. Tetrahedron Lett.  1984,  25:  4505 
• 17f Grigg R. Sridharan V. Terrier C. Tetrahedron Lett.  1996,  37:  4221 
• 17g Grigg R. Savic V. Tetrahedron Lett.  1996,  37:  6565 
• 17h Larock RC. Zenner JM. J. Org. Chem.  1995,  60:  482 
• 17i Besson L. Bazin J. Gore J. Cazes B. Tetrahedron Lett.  1994,  35:  2881 
• 17j Cazes B. Pure Appl. Chem.  1990,  62:  1867 
• 17k Larock RC. Berrios-Pena NG. Fried CA. J. Am. Chem. Soc.  1991,  56:  2615 
• 18a Doucet H. Bruneau C. Dixneuf PH. Synlett  1997,  7:  807 
• 18b Syper L. Tetrahedron  1987,  43:  2853 
• 19 Salaün J. Marguerite J. Org. Synth. Coll. Vol. VII   John Wiley & Sons; London: 1990.  p.131 
• 20 Militzer H.-C. Dissertation   Universität Hamburg; Germany: 1990. 
• 21 Bruneau C. Kabouche Z. Neveux M. Seiller B. Dixneuf PH. Inorg. Chim. Acta  1994,  222:  155 
• 22 Lechevallier A. Huet F. Conia JC. Tetrahedron  1983,  39:  3329 
• 23a Salaün J. Almirantis Y. Tetrahedron  1983,  39:  2441 
• 23b Barnier J.-P. Karkour B. Salaün J. J. Chem. Soc., Chem. Commun.  1985,  1270 
• Cyclopropylethyne is commercially available and can easily be prepared in two to three steps:
• 24a Corley EG. Thomson AS. Huntington M. Org. Synth. Coll. Vol. X   John Wiley & Sons; London: 2004.  p.456 
• 24b

  See ref. 9f.

• 26 Ruppin C. Dixneuf PH. Tetrahedron Lett.  1986,  27:  6323 
• 27 1-Ethynylcyclopropanol (14) had previously been prepared from cyclopropanone ethyl hemiacetal, yet only in 21% yield; see: Wasserman HH. Cochoy RE. Baird MS. J. Am. Chem. Soc.  1969,  91:  2375 
• 28a Salaün J. J. Org. Chem.  1976,  41:  1237 
• 28b Salaün J. Bennani F. Compain JC. Fadel A. J. Org. Chem.  1980,  45:  4129 

12

The ring closure in this sequence^9f is best performed with LiHMDS, not with LDA.^9g Subsequent complete isomerization of the cis- to the trans-isomer in the initially obtained mixture is then achieved by treatment with LDA for 5 min.

25

It is noteworthy that the amount of catalyst is critical in this reaction. When less than 1 mol% of C was used, an increasing amount of the 1-substituted vinyl ester was observed. The prolonged reaction time allowed the catalyst to alter (be oxidized?) and obviously the altered species still catalyzes the addition but with diminished selectivity.