Efficient and Divergent Synthesis of Functionalized Cyclopropanes via Iodoform Reaction

Abstract

Efficient and divergent one-pot synthesis of cyclopropyl amides and esters from readily available 1-acetylcyclopropanes via iodoform reaction based on the selection of reaction conditions is reported. A series of substituted cyclopropyl amides were synthesized from 1-acetylcyclopropanes, iodine, and ammonia in water in the presence of K₂CO₃ in good yields, whereas substituted cyclopropyl esters were obtained from the reaction of 1-acetylcyclopropanes with iodine and alcohols in the presence of DBU.

cyclopropanes - iodoform reaction - iodine - amide - water­

References

For reviews on cyclopropanes, see:

<A NAME="RF110811SS-1A">1a</A> Wong HNC. Hon MY. Tse CW. Yip YC. Tanko J. Hudlicky T. Chem. Rev.  1989,  89:  165 

<A NAME="RF110811SS-1B">1b</A> Kulinkovich OG. Chem. Rev.  2003,  103:  2597 

<A NAME="RF110811SS-1C">1c</A> Brackmann F. de Meijere A. Chem. Rev.  2007,  107:  4493 

<A NAME="RF110811SS-1D">1d</A> Gnad F. Reiser O. Chem. Rev.  2003,  103:  1603 

<A NAME="RF110811SS-1E">1e</A> Noyori R. Angew. Chem. Int. Ed.  2002,  41:  2008 

<A NAME="RF110811SS-2A">2a</A> Vinogradov MG. Kaigorodova LN. Chel’tsova-Bebutova GV. Gorshkova LS. Starostin EK. Nikishin GL. Ignatenko AV. Shapiro EA. Russ. Chem. Bull.  1995,  44:  167 

<A NAME="RF110811SS-2B">2b</A> Kaneko H. J. Agric. Food Chem.  2011,  59:  2786 

<A NAME="RF110811SS-2C">2c</A> Graham DW. Ashton WT. Barash L. Brown JE. Brown RD. Canning LF. Chen A. Springer JP. Rogers EF. J. Med. Chem.  1987,  30:  1074 

<A NAME="RF110811SS-2D">2d</A> Krief A. Froidbisea A. Tetrahedron  2004,  60:  7637 

For reviews, see:

<A NAME="RF110811SS-3A">3a</A> Hoveyda AH. Evans DA. Fu GC. Chem. Rev.  1993,  93:  1307 

<A NAME="RF110811SS-3B">3b</A> Charette AB. Marcoux J.-F. Synlett  1995,  1197 

<A NAME="RF110811SS-3C">3c</A> Lautens M. Klute W. Tam W. Chem. Rev.  1996,  96:  49 

<A NAME="RF110811SS-3D">3d</A> Charette AB. Lebel H. In Comprehensive Asymmetric Catalysis   Jacobsen EN. Pfaltz A. Yamamoto H. Springer-Verlag; Berlin: 1999.  Chap. 16.3.

<A NAME="RF110811SS-3E">3e</A> Lebel H. Marcoux J.-F. Molinaro C. Charette AB. Chem. Rev.  2003,  103:  977 

For references, see:

<A NAME="RF110811SS-4A">4a</A> Simmons HE. Smith RD. J. Am. Chem. Soc.  1958,  80:  5323 

<A NAME="RF110811SS-4B">4b</A> Simmons HE. Smith RD. J. Am. Chem. Soc.  1959,  81:  4256 

<A NAME="RF110811SS-4C">4c</A> Rawson RJ. Harrison IT. J. Org. Chem.  1970,  35:  2057 

<A NAME="RF110811SS-4D">4d</A> Nishimura J. Furukawa J. Kawabata N. Kitayama M. Tetrahedron  1971,  27:  1799 

<A NAME="RF110811SS-4E">4e</A> Friedrich EC. Lunetta SE. Lewis EJ. J. Org. Chem.  1989,  54:  2388 

<A NAME="RF110811SS-4F">4f</A> Charette AB. Marcoux J.-F. Molinaro C. Beauchemin A. Brochu C. Isabel E. J. Am. Chem. Soc.  2000,  122:  4508 

<A NAME="RF110811SS-5A">5a</A> Shimamoto K. Ishida M. Shinozaki H. Ohfune Y.
J. Org. Chem.  1991,  56:  4167 

<A NAME="RF110811SS-5B">5b</A> Shimamoto K. Ohfune Y. Tetrahedron Lett.  1989,  30:  3802 

<A NAME="RF110811SS-5C">5c</A> Hanessian S. Murray PJ. J. Org. Chem.  1987,  52:  1170 

<A NAME="RF110811SS-5D">5d</A> Vangveravong S. Nichols DE. J. Org. Chem.  1995,  60:  3409 

<A NAME="RF110811SS-5E">5e</A> Pietruszka J. Widenmeyer M. Synlett  1997,  977 

<A NAME="RF110811SS-5F">5f</A> Luithle JEA. Pietruszka J. J. Org. Chem.  1999,  64:  8287 

<A NAME="RF110811SS-5G">5g</A> Pietruszka J. Witt A. J. Chem. Soc., Perkin Trans. 1  2000,  4293 

<A NAME="RF110811SS-5H">5h</A> Luithle JEA. Pietruszka J. J. Org. Chem.  2000,  65:  9194 

<A NAME="RF110811SS-6A">6a</A> de Meijere A. Bagutski V. Zeuner F. Fischer UK. Rheinberger V. Moszner N. Eur. J. Org. Chem.  2004,  3669 

<A NAME="RF110811SS-6B">6b</A> Yang Y. Shi M. J. Org. Chem.  2005,  70:  8645 

<A NAME="RF110811SS-6C">6c</A> Su J. Xiong J. Liang S. Qiu G. Feng X. Teng H. Wu L. Hu X. Synth. Commun.  2006,  36:  693 

<A NAME="RF110811SS-6D">6d</A> Ronsisvalle G. Marrazzo A. Prezzavento O. Pasquinucci L. Falcucci B. Toro RD. Spampinato S. Bioorg. Med. Chem.  2000,  8:  1503 

<A NAME="RF110811SS-7A">7a</A> Pan W. Dong D. Wang K. Zhang J. Wu R. Xiang D. Liu Q. Org. Lett.  2007,  9:  2421 

<A NAME="RF110811SS-7B">7b</A> Fu X. Huang P. Zhou G. Hu Y. Dong D. Tetrahedron  2011,  67:  6347 

<A NAME="RF110811SS-7C">7c</A> Wang K. Fu X. Liu J. Liang Y. Dong D. Org. Lett.  2009,  11:  1015 

<A NAME="RF110811SS-7D">7d</A> Wang K. Xiang D. Liu J. Pan W. Dong D. Org. Lett.  2008,  10:  1691 

For Iodoform reactions, see:

<A NAME="RF110811SS-8A">8a</A> Fuson RC. Bull BA. Chem. Rev.  1934,  15:  275 

<A NAME="RF110811SS-8B">8b</A> Fuson RC. Tullock CW. J. Am. Chem. Soc.  1934,  56:  1638 

<A NAME="RF110811SS-8C">8c</A> Arnold RT. Buckles R. Stoltenberg J. J. Am. Chem. Soc.  1944,  66:  208 

For the conversion of acetyl into amide and ester group, see:

<A NAME="RF110811SS-8D">8d</A> Cao L. Ding J. Gao M. Wang Z. Li J. Wu A. Org. Lett.  2009,  11:  3810 

<A NAME="RF110811SS-8E">8e</A> Yin G. Gao M. Wang Z. Wu Y. Wu A. Bull. Chem. Soc. Jpn.  2008,  81:  369 

<A NAME="RF110811SS-9">9</A> For the preparation of 1-acetyl-1-carbamoylcyclopropanes, see: Zhang Z. Zhang Q. Sun S. Xiong T. Liu Q. Angew. Chem. Int. Ed.  2007,  46:  1726 

<A NAME="RF110811SS-10A">10a</A> Aqueous-Phase Organometallic Catalysis: Concepts and Applications   Cornils B. Herrmann WA. Wiley-VCH; Weinheim: 1998. 

<A NAME="RF110811SS-10B">10b</A> Organic Synthesis in Water   Grieco PA. Blackie Academic and Professional; London: 1998. 

<A NAME="RF110811SS-10C">10c</A> Organic Reactions in Aqueous Media   Li C.-J. Chan T.-H. Wiley; New York: 1997. 

<A NAME="RF110811SS-10D">10d</A> Kobayashi S. Manabe K. In Stimulating Concepts in Chemistry   Shibasaki M. Stoddart JF. Vögtle F. Wiley-VCH; Weinheim: 2000. 

<A NAME="RF110811SS-11A">11a</A> Li CJ. Chem. Rev.  1993,  93:  2023 

<A NAME="RF110811SS-11B">11b</A> Fringuelli F. Piermatti O. Pizzo F. Vaccaro L. Eur. J. Org. Chem.  2001,  439 

<A NAME="RF110811SS-11C">11c</A> Kobayashi S. Manabe K. Acc. Chem. Res.  2002,  35:  209 

<A NAME="RF110811SS-12A">12a</A> Manabe K. Mori Y. Kobayashi S. Synlett  1999,  1401 

<A NAME="RF110811SS-12B">12b</A> Manabe K. Kobayashi S. Org. Lett.  1999,  1:  1965 

<A NAME="RF110811SS-12C">12c</A> Otto S. Engberts JBSN. Kwak JCT. J. Am. Chem. Soc.  1998,  120:  9517 

<A NAME="RF110811SS-12D">12d</A> Rispens T. Engberts JBSN. Org. Lett.  2001,  3:  941 

<A NAME="RF110811SS-12E">12e</A> Manabe K. Sun XM. Kobayashi S. J. Am. Chem. Soc.  2001,  123:  10101 

<A NAME="RF110811SS-12F">12f</A> Ouyang Y. Dong D. Yu H. Liang Y. Liu Q. Adv. Synth. Catal.  2006,  348:  206 

<A NAME="RF110811SS-13">13</A>

The relative configurations of cis -1k, trans -1l, cis -2k, and trans -2l were determined by NOESY, see Supporting Information.

For selected work on the conversion of amide into cyano group, see:

<A NAME="RF110811SS-14A">14a</A> Mowry DT. Chem. Rev.  1948,  42:  189 

<A NAME="RF110811SS-14B">14b</A> Rickborn B. Jensen FR. J. Org. Chem.  1962,  27:  4608 

<A NAME="RF110811SS-14C">14c</A> Lehnert W. Tetrahedron Lett.  1971,  19:  1501 

<A NAME="RF110811SS-14D">14d</A> Ellzey SE. Mack CH. Connick WJ. J. Org. Chem.  1967,  32:  846 

For selected examples on ring-opening or ring-enlargement reactions of cyclopropanes, see:

<A NAME="RF110811SS-15A">15a</A> Bernard AM. Frongia A. Piras PP. Secci F. Spiga M. Org. Lett.  2005,  7:  4565 

<A NAME="RF110811SS-15B">15b</A> Ogoshi S. Nagata M. Kurosawa H. J. Am. Chem. Soc.  2006,  128:  5350 

<A NAME="RF110811SS-15C">15c</A> Liu L. Montgomery J.
J. Am. Chem. Soc.  2006,  128:  5348 

<A NAME="RF110811SS-15D">15d</A> Ma S. Zhang J. Angew. Chem. Int. Ed.  2003,  42:  183 

For selected references on Vilsmeier reagents, see:

<A NAME="RF110811SS-16A">16a</A> Marson CM. Tetrahedron  1992,  48:  3659 

<A NAME="RF110811SS-16B">16b</A> Meth-Cohn O. Tarnowski B. Adv. Heterocycl. Chem.  1982,  31:  207 

<A NAME="RF110811SS-16C">16c</A> Reichardt C. J. Prakt. Chem.  1999,  341:  609 

<A NAME="RF110811SS-16D">16d</A> Gangadasu B. Narender P. Kumar SB. Ravinder M. Rao BA. Ramesh C. Raju BC. Rao VJ. Tetrahedron  2006,  62:  8398 

<A NAME="RF110811SS-16E">16e</A> Thomas AD. Asokan CV. Tetrahedron  2004,  60:  5069 

<A NAME="RF110811SS-17A">17a</A> Johnson CR. Lockard JP. Kennedy ER. J. Org. Chem.  1980,  45:  264 

<A NAME="RF110811SS-17B">17b</A> Zhang Z. Xue C. Liu X. Zhang Q. Liu Q. Tetrahedron  2011,  67:  7081