Synlett, Table of Contents Synlett 2014; 25(17): 2467-2470DOI: 10.1055/s-0034-1379009 letter © Georg Thieme Verlag Stuttgart · New York Synthesis of Tenuifolin through Intramolecular Nicholas Reaction Sinisa Djurdjevic Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON, N9B 3P4, Canada Fax: +1(519)9737098 Email: jgreen@uwindsor.ca , James R. Green* Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON, N9B 3P4, Canada Fax: +1(519)9737098 Email: jgreen@uwindsor.ca › Author Affiliations Recommend Article Abstract Buy Article All articles of this category Abstract The synthesis of the Cinnamomum homosesquiterpenoid tenuifolin has been accomplished by way of an intramolecular Nicholas reaction of the [Co2(CO)6] complex of an alkyne-substituted biaryl for construction of the seven-membered ring. The cyclization features the reaction of a nonactivated arene ring with the propargyldicobalt cation to give the dibenzocycloheptyne-Co2(CO)6. Key words Key wordsalkynes - total synthesis - carbocation - fused-ring systems - electrophilic aromatic substitution - transition metals Full Text References References and Notes 1a Lin R.-J, Cheng M.-J, Huang J.-C, Lo W.-L, Yeh Y.-T, Yen C.-M, Lu C.-M, Chen C.-Y. J. Nat. Prod. 2009; 72: 1816 1b Lin IJ, Yeh HC, Cham TM, Chen CY. Chem. Nat. Compd. 2011; 47: 43 1c Subehan S, Kadota S, Tezuka Y. Planta Med. 2008; 74: 1474 1d Chen C.-Y, Yang W.-L, Hsui Y.-R. Nat. Prod. Res. 2010; 24: 423 1e Chia Y.-C, Yeh H.-C, Yeh Y.-T, Chen C.-Y. Chem. Nat. Comp. 2011; 47: 220 1f Chen C.-Y, Hong Z.-L, Yang W.-L, Wub M.-H, Huang J.-C, Lee J.-Y. Nat. Prod. Res. 2012; 26: 1218 1g Lin H.-C, Lee S.-S. J. Nat. Prod. 2012; 75: 1735 1h Chen H.-L, Yang W.-L, Li Y.-P, Kang Y.-F, Wu H.-M, Chen C.-L, Chen C.-T, Chen W.-Y, Chen S.-Y, Chen C.-Y. J. Med. Med. Sci. 2012; 3: 90 1i Lee C.-H, Kuo C.-N, Chen H.-L, Chen C.-Y. Nat. Prod. Res. 2013; 27: 988 2a Tang C, Li Z, Wang Y, Xu J, Kong L, Yao H, Wu X. Tetrahedron Lett. 2011; 52: 3275 2b See also: Hackelöer K, Schnakenburg G, Waldvogel SR. Eur. J. Org. Chem. 2011; 6314 3a Green JR. Synlett 2012; 23: 1271 3b Green JR. Eur. J. Org. Chem. 2008; 6053 3c Amiralaei S, Green JR. Chem. Commun. 2008; 4971 3d Ding Y, Green JR. Synlett 2005; 271 3e Green JR. Synlett 2001; 353 3f Lu Y, Green JR. Synlett 2001; 243 3g Patel MM, Green JR. Chem. Commun. 1999; 509 3h Green JR. Chem. Commun. 1998; 1751 4a Schreiber SL, Sammakia T, Crowe WE. J. Am. Chem. Soc. 1986; 108: 3128 4b Iwasawa N, Satoh H. J. Am. Chem. Soc. 1999; 121: 7951 4c Tanino K, Shimizu T, Miyama M, Kuwajima I. J. Am. Chem. Soc. 2000; 122: 6116 4d Iwasawa N, Sakurada F, Iwamoto M. Org. Lett. 2000; 2: 871 4e Tanino K, Kondo F, Shimizu T, Miyashita M. Org. Lett. 2002; 4: 2217 4f Carbery DR, Reignier S, Myatt JW, Miller ND, Harrity JP. A. Angew. Chem. Int. Ed. 2002; 41: 2584 4g Tanino K, Onuki K, Asano K, Miyashita M, Nakamura T, Takahashi Y, Kuwajima I. J. Am. Chem. Soc. 2003; 125: 1498 4h Young DG. J, Burlison JA, Peters U. J. Org. Chem. 2003; 68: 3494 4i Golovko LJ, Hope-Weeks MJ, Mays MJ, McPartlin M, Sloan AM, Woods AD. New J. Chem. 2004; 28: 527 4j Iwasawa N, Inaba K, Nakayama S, Aoki M. Angew. Chem. Int. Ed. 2005; 44: 7447 4k Olier C, Gastaldi S, Christie SD. R, Bertrand MP. Synlett 2007; 423 4l Inaba K, Takaya J, Iwasawa N. Chem. Lett. 2007; 36: 474 4m For the corresponding ethers, see: Baba T, Huang G, Isobe M. Tetrahedron 2003; 59: 6851; and references therein 4n For the corresponding amides, see: Closser KD, Quintal MM, Shea KM. J. Org. Chem. 2007; 74: 2680 5a Djurdjevic S, Yang F, Green JR. J. Org. Chem. 2010; 75: 8241 5b Djurdjevic S, Green JR. Org. Lett. 2007; 9: 5505 For recent Nicholas reaction reviews, see: 6a Kann N. Curr. Org. Chem. 2012; 16: 322 6b Shea KM In Name Reactions for Homologations . Li JJ. Wiley; Hoboken: 2009. Part 1 284 6c Diaz DD, Betancort JM, Martín VS. Synlett 2007; 343 6d Teobald BJ. Tetrahedron 2002; 58: 4133 6e Green JR. Curr. Org. Chem. 2001; 5: 809 For the original Nicholas publications, see: 7a Nicholas KM, Pettit R. J. Organomet. Chem. 1972; 44: C21 7b Connor RE, Nicholas KM. J. Organomet. Chem. 1977; 125: C21 7c Lockwood RF, Nicholas KM. Tetrahedron Lett. 1977; 4163 7d Nicholas KM. Acc. Chem. Res. 1987; 20: 207 8a Kuhn O, Rau H, Mayr H. J. Am. Chem. Soc. 1998; 120: 900 8b Mayr H, Kempf B, Ofial AR. Acc. Chem. Res. 2003; 36: 66 8c There is anecdotal evidence that suggests entropic factors assist similar intramolecular reactions of related complexes. 9a Wolfe JP, Nakhia JS In Name Reactions for Homlogations . Li JJ. Wiley; Hoboken: 2009. Part 1 163 9b Valente C, Organ MG In Boronic Acids . Hall DG. Wiley-VCH; Weinheim: 2011. 2nd ed. 213 10a Eymery F, Iorga B, Savignac P. Synthesis 2000; 185 10b Chalifoux WA, Tykwinski RR. Chem. Rec. 2006; 6: 169 10c Han X In Name Reactions for Homlogations . Li JJ. Wiley; Hoboken: 2009. Part 1 393 11 Kira K, Tanda H, Hamajima A, Baba T, Takai S, Isobe M. Tetrahedron 2002; 58: 6485 12a Chamberlin AR, Bloom SH. Org. React. 1990; 39: 1 12b Wolfe JP In Name Reactions for Functional Group Transformation . Li JJ, Corey EJ. Wiley; Hoboken: 2007: 405 13 Murray RW, Singh M. Org. Synth. 1997; 74: 91 14 Campbell MM, Abbas N, Sainsbury M. Tetrahedron 1985; 41: 5637 15 Use of Bu3SnCH2OH/Pd(PPh3)4 afforded tenuifolin in modest yield (35%). 16a Kosugi M, Sumiya T, Ohhashi K, Sano H, Migita T. Chem. Lett. 1985; 997 16b Murai N, Yonaga M, Tanaka K. Org. Lett. 2012; 14: 1278 17 Attempted use of paraformaldehyde as electrophile gave largely decomposed material, along with small amounts of 14. 18 Crossland I. Org. Synth. 1981; 60: 6 19 By comparison, the synthetic route developed by Yao, Wu and co-workers (see ref. 2a) gave 15% overall yield in seven steps. Supplementary Material Supplementary Material Supporting Information
