Abstract
Lewis or Brønsted acid-mediated intramolecular rearrangement of VDCPs, and the reactions of VDCPs with acetals, aldehydes, ketones, imines, activated alkenes, nitriles, acyl chlorides, and alcohols are described in this chapter.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
References
Shi M, Shao LX, Lu JM, Wei Y, Mizuno K, Maeda H (2010) Chemistry of vinylidenecyclopropanes. Chem Rev 110:5883–5913
Pasto DJ, Miles MF (1976) Electrophilic addition reactions of alkenylidenecyclopropanes. Formation of highly substituted, nonplanar butadienes. J Org Chem 41:425–432
Pasto DJ, Gontarz JA (1969) The mechanism of the reduction of organomercurials with sodium borohydride. J Am Chem Soc 91:719–721
Gray GA, Jackson WR (1969) Sodium borohydride reduction of oxymercury compounds. J Am Chem Soc 91:6205–6207
Whitesides GM, Filippo JS Jr (1970) The mechanism of reduction of alkylmercuric halides by metal hydrides. J Am Chem Soc 92:6611–6624
DePuy CR, Van Lanen RJ (1974) Reactions of cyclopropanols with halogenating agents and other electrophiles. J Org Chem 39:3360–3365
Pasto DJ, Smorada RL, Turini BL, Wampfler DJ (1976) Electrophilic and radical addition reactions of a bisalkylidenecyclopropane. J Org Chem 41:432–438
Xu GC, Ma M, Liu LP, Shi M (2005) A novel rearrangement of arylvinylidenecyclopropanes to naphthalene derivatives catalyzed by Lewis acids or Brønsted acids. Synlett 1869–1872
Xu GC, Liu LP, Lu JM, Shi M (2005) Lewis acid-catalyzed rearrangement of multi-substituted arylvinylidenecyclopropanes. J Am Chem Soc 127:14552–14553
Zhang YP, Lu JM, Xu GC, Shi M (2007) Lewis-acid-catalyzed rearrangement of arylvinylidenecyclopropanes: significant influence of substituents and electronic nature of aryl groups. J Org Chem 72:509–516
Lu JM, Shi M (2007) Montmorillonite K-10-catalyzed intramolecular rearrangement of vinylidenecyclopropanes. Tetrahedron 63:7545–7549
Siehl HU, Aue DH (1997) In: Rappoport Z, Stang PJ (eds) Dicoordinated carbocations. Wiley, New York, pp 137–138
The stabilizing effect of cyclopropyl substituents on carbocations was well documented, see: Olah GA, Reddy VP, Surya Prakash GK (1992) Long-lived cyclopropylcarbinyl cations. Chem Rev 92:69–95
Bollinger JM, Brinich JM, Olah GA (1970) Stable carbonium ions. XCVI. Propadienylhalonium ions and 2-haloallyl cations. J Am Chem Soc 92:4025–4033
Carey FA, Sundberg RJ (1998) Advanced organic chemistry, 5th edn. Plenum Press, New York, pp 221, 419
Carey FA, Tremper HS (1969) Carbonium ion-silane hydride transfer reactions. III. Cyclopropylmethyl cations. J Am Chem Soc 91:2967–2972
Fleming I (2001) Improving the Friedel–Crafts reaction. Chemtracts: Org Chem 14:405–406
For the mechanism of the 1,3-proton shift, see: Carey FA, Sundburg RJ (1990) Advanced organic chemistry. 3rd edn. Plenum Press, New York, pp 609–613
Shi M, Wu L, Lu JM (2008) Gold(I)-catalyzed intramolecular rearrangement of vinylidenecyclopropanes. J Org Chem 73:8344–8347
Li W, Shi M, Li YX (2009) Brønsted acid mediated novel rearrangement of diarylvinylidenecyclopropanes and mechanistic investigations based on DFT calculations. Chem Eur J 15:8852–8860
Huang X, Su CL, Liu QY, Song YT (2008) A facile access to medium- and large-size naphthalenacarbocycles via Lewis acid mediated ring-expansion reaction of bicyclic vinylidenecyclopropanes. Synlett 229–232
Lu JM, Shi M (2006) Lewis acid catalyzed reaction of arylvinylidenecyclopropanes with acetals: a facile synthetic protocol for the preparation of indene derivatives. Org Lett 8:5317–5320
Su CL, Liu QY, Ni Y, Huang X (2009) An efficient synthesis of polysubstituted tetrahydrofuran and indene derivatives via the Lewis acid-mediated cycloaddition of VCPs with aldehydes. Tetrahedron Lett 50:4381–4383
Su CL, Huang X (2009) Lewis acid-mediated selective cycloadditions of vinylidenecyclopropanes with aromatic aldehydes: an efficient protocol for the synthesis of benzo[c]fluorene, furan and furo[2,3-b]furan derivatives. Adv Synth Catal 351:135–140
Su CL, Huang X, Liu QY, Huang X (2009) Facile synthesis of tetrahydrofurans from cycloadditions of vinylidenecyclopropanes with aldehydes and further transformations for the construction of furan, indene, and benzo[c]fluorene derivatives. J Org Chem 74:8272–8279
Lu JM, Shi M (2008) Lewis acid catalyzed reactions of vinylidenecyclopropanes with activated carbon-oxygen double bond: a facile synthetic protocol for functionalized tetrahydrofuran and 3,6-dihydropyran derivatives. J Org Chem 73:2206–2210
Lu JM, Shi M (2007) Lewis acid catalyzed reaction of arylvinylidenecyclopropanes with ethyl (arylimino)acetates: a facile synthetic protocol for pyrrolidine and 1,2,3,4-tetrahydroquinoline derivatives. Org Lett 9:1805–1808
When N-aryl substituted imines were used as the substrates, similar transformations can be obtained in very low yields, see: Stepakov AV, Larina AG, Molchanov AP, Stepakova LV, Starova GL, Kostikov RR (2007) Reaction of vinylidenecyclopropanes with aromatic imines in the presence of Lewis acids. Russ J Org Chem 43:40–49
Prato and Scorrano’s group reported BF3 .OEt2-catalyzed cycloaddition reaction of aryliminoacetates with electron-rich olefins to give tetrahydroquinoline derivatives, see: Borrione E, Prato M, Scorrano G, Stivanello M, Lucchini V (1988) Synthesis and cycloaddition reactions of ethyl glyoxylate imines. Synthesis of substituted furo-[3,2-c]quinolines and 7H-indeno[2,1-c]quinolines. J Heterocycl Chem 25:1831–1835
Regás D, Afonso MM, Rodríguez ML, Antonio Palenzuela J (2003) Synthesis of octahydroquinolines through the Lewis acid catalyzed reaction of vinyl allenes and imines. J Org Chem 68:7845–7852
Hayashi Y, Shibata T, Narasaka K (1990) Ene reaction of allenyl sulfides with aldehydes and Schiffs bases catalyzed by Lewis acids. Chem Lett 1693–1696
Xu B, Shi M (2003) Lewis acid-catalyzed reaction of allenes with activated ketone. Synlett 1639–1642
Chevrier B, Weiss R (1974) Structures of the intermediate complexes in Friedel–Crafts acylations. Angew Chem Int Ed Engl 13:1–10
Kobayashi has concluded that this type of aza-Diels–Alder reaction proceeded via a stepwise mechanism, see: Kobayashi S, Ishitani H, Nagayama S (1995) Lanthanide triflate catalyzed imino Diels–Alder reactions; convenient syntheses of pyridine and quinoline derivatives. Synthesis 1195–1202
Shi M, Shao LX, Xu B (2003) The Lewis acids catalyzed aza-Diels–Alder reaction of methylenecyclopropanes with imines. Org Lett 5:579–582
Shao LX, Shi M (2003) Montmorillonite KSF-catalyzed one-pot, three-component, aza-Diels–Alder reactions of methylenecyclopropanes with arenecarbaldehydes and arylamines. Adv Synth Catal 345:963–966
Zhu ZB, Shao LX, Shi M (2009) Brønsted acid or solid acid catalyzed aza-Diels–Alder reactions of methylenecyclopropanes with ethyl (arylimino)acetates. Eur J Org Chem 2576–2580
Lu JM, Zhu ZB, Shi M (2009) Lewis acid or Brønsted acid catalyzed reactions of vinylidene cyclopropanes with activated carbon-nitrogen, nitrogen–nitrogen, and iodine-nitrogen double-bond-containing compounds. Chem Eur J 15:963–971
Li Z, Conser KR, Jacobsen EN (1993) Asymmetric alkene aziridination with readily available chiral diimine-based catalysts. J Am Chem Soc 115:5326–5327
Li W, Shi M (2009) A catalytic method for the preparation of polysubstituted cyclopentanes: [3 + 2] cycloaddition of vinylidenecyclopropanes with activated olefins catalyzed by triflic imide. J Org Chem 74:856–860
Li W, Shi M (2009) Triflic imide-catalyzed cascade cycloaddition and Friedel–Crafts reaction of diarylvinylidenecyclopropanes with ethyl 5,5-diarylpenta-2,3,4-trienoate. Org Biomol Chem 7:1775–1777
Li W, Shi M (2008) Brønsted acid TfOH-mediated [3 + 2] cycloaddition reactions of diarylvinylidenecyclopropanes with nitriles. J Org Chem 73:4151–4154
For related results of methylenecyclopropanes from Shi’s group, see: Huang JW, Shi M (2004) Brønsted acid TfOH-mediated reactions of methylenecyclopropanes with nitriles. Synlett 2343–2346 and references therein
Shi M, Tian GQ (2006) Brønsted acid TfOH-mediated reactions of 2-(arylmethylene)cyclopropylcarbinols with acetonitrile. Tetrahedron Lett 47:8059–8062
Booth BL, Noori GFM (1980) The chemistry of nitrilium salts. Part l. Acylation of phenols and phenol ethers with nitriles and trifluoromethanesulphonic acid. J Chem Soc Perkin Trans 1:2894–2900
Amer MI, Booth BL, Noori GFM, Proença MFJRP (1983) The chemistry of nitrilium salts. Part 3. The importance of triazinium salts in Houben-Hoesch reactions catalyzed by trifluoromethanesulphonic acid. J Chem Soc Perkin Trans 1:1075–1082
Shi M, Wu L, Lu JM (2008) AlCl3-mediated tandem Friedel–Crafts reactions of vinylidenecyclopropanes with acyl chlorides: a facile synthetic method for the construction of 1-[2-(2,2-diarylvinyl)-1-phenyl-3H-inden-5-yl]ethanone derivatives. Tetrahedron 64:3315–3321
For pioneering work on the reactions of methylenecyclopropanes with acyl chloride in the presence of AlCl3, see: Huang X, Yang YW (2007) Acylation of alkylidenecyclpropanes for the facile synthesis of α,β-unsaturated ketone and benzofulvene derivatives with high stereoselectivity. Org Lett 9:1667–1670
Shi M, Yao LF (2008) Lewis acid catalyzed reactions of diarylvinylidenecyclopropanes and 1,1,3-triarylprop-2-yn-1-ols or their methyl ethers. Chem Eur J 14:8725–8731
Swaminathan S, Narayanan KV (1971) The Rupe and Meyer-Schuster rearrangements. Chem Rev 71:429–438
Edens M, Boerner D, Chase CR, Nass D, Schiavelli MD (1977) Mechanism of the Meyer-Schuster rearrangement. J Org Chem 42:3403–3408
Yao LF, Shi M (2009) Nd(OTf)3-catalyzed cascade reactions of vinylidenecyclopropanes with enynol: a new method for the construction of the 5-7-6 tricyclic framework and its scope and limitations. Eur J Org Chem 4036–4040
Yao LF, Shi M (2009) Lewis acid catalyzed cascade reactions of 1,6-diynes and 1,6-enynes with vinylidenecyclopropanes. Chem Eur J 15:3875–3881
Michelet V, Toullec PY, Genêt JP (2008) Cycloisomerization of 1, n-enynes: challenging metal-catalyzed rearrangements and mechanistic insights. Angew Chem Int Ed 47:4268–4315
Bruneau C (2005) Electrophilic activation and cycloisomerization of enynes: a new route to functional cyclopropanes. Angew Chem Int Ed 44:2328–2334
Yuan W, Shi M (2010) Reactions of vinylidenecyclopropanes with xanthydrol and xanthenes. Tetrahedron 66:7104–7111
For pioneering work with bis(4-alkoxyphenyl)methanols as the electrophiles, please see: Wu L, Shi M, Li YX (2010) BF3 .OEt2-catalyzed intermolecular reactions of vinylidenecyclopropanes with bis(p-alkoxyphenyl)methanols: a novel cationic 1,4-aryl-migration process. Chem Eur J 16:5163–5172
Li W, Yuan W, Pindi S, Shi M, Li GG (2010) Au/Ag-catalyzed intramolecular ring-opening of vinylidene-cyclopropanes (VDCPs): an easy access to functional tetrahydropyrans. Org Lett 12:920–923
Hyland CJT, Hegedus LS (2006) Gold-catalyzed and N-iodosuccinimide-mediated cyclization of γ-substituted allenamides. J Org Chem 71:8658–8660
Morita N, Krause N (2006) The first gold-catalyzed C-S bond formation: cycloisomerization of α-thioallenes to 2,5-dihydrothiophenes. Angew Chem Int Ed 45:1897–1899
Sromek AW, Rubina M, Gevorgyan V (2005) 1,2-Halogen migration in haloallenyl ketones: regiodivergent synthesis of halofurans. J Am Chem Soc 127:10500–10501
Nishina N, Yamamoto Y (2006) Gold-catalyzed intermolecular hydroamination of allenes with arylamines and resulting high chirality transfer. Angew Chem Int Ed 45:3314–3317
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
Copyright information
© 2012 The Author(s)
About this chapter
Cite this chapter
Shao, L., Lu, J., Shi, M. (2012). Lewis or Brønsted Acid-Mediated Transformations of VDCPs. In: Chemical Transformations of Vinylidenecyclopropanes. SpringerBriefs in Molecular Science(). Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-27573-9_2
Download citation
DOI: https://doi.org/10.1007/978-3-642-27573-9_2
Published:
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-27572-2
Online ISBN: 978-3-642-27573-9
eBook Packages: Chemistry and Materials ScienceChemistry and Material Science (R0)