Synthesis 2019; 51(12): 2515-2522
DOI: 10.1055/s-0037-1611807
special topic
© Georg Thieme Verlag Stuttgart · New York

Ruthenium-Catalyzed Directed C(3)–H Olefination of N-Acetyl-1,2-dihydroisoquinolines: A Method to Achieve C3-Olefinated Isoquinolines

Riki Das
,
Nandkishor Prakash Khot
,
Akanksha Santosh Deshpande
,
SERB-India (EMR/2016/004298/OC) and CSIR-India [02(205)/14/EMR-II] are gratefully acknowledged for the research funding.
Further Information

Publication History

Received: 15 February 2019

Accepted after revision: 02 April 2019

Publication Date:
15 April 2019 (eFirst)

§ Equal contribution

Published as part of the Special Topic Ruthenium in Organic Synthesis

Abstract

A unique approach to achieve regioselective C(3)–H olefination of isoquinolines under ruthenium-catalyzed conditions has been developed. The acetyl group of N-acetyl-1,2-dihydroisoquinoline acts as a directing group for this C–H olefination strategy. Removal of the acetyl directing group by a simple method leads to a quick access to C-3 olefinated isoquinolines. The methodology is a very good alternative to the traditional Heck reaction and substrates with halogen substituents are very good candidates for the transformation.

Supporting Information

 
  • References

  • 1 Present address: Department of Chemistry, University of Minnesota, 207 Pleasant Street S.E., Minneapolis, MN 55455-0431, USA.
    • 2a Menachery MD, Lavanier GL, Wetherly ML, Guinaudeau H, Shamma M. J. Nat. Prod. 1986; 49: 745
    • 2b Croisy-Delcey M, Croisy A, Carrez D, Huel C, Chiaroni A, Ducrot P, Bisagni E, Jin L, Leclercq G. Bioorg. Med. Chem. 2000; 8: 2629
    • 2c Rinehart KL. Med. Res. Rev. 2000; 20: 1
    • 2d Casellas P, Galiegue S, Basile AS. Neurochem. Int. 2002; 40: 475
    • 2e Kartsev VG. Med. Chem. Res. 2004; 13: 325
    • 2f Bentley KW. Nat. Prod. Rep. 2006; 23: 444
    • 2g Bhadra K, Kumar GS. Med. Res. Rev. 2011; 31: 821
    • 3a Collado D, Perez-Inestrosa E, Suau R, Desvergne J.-P, Bouas-Laurent H. Org. Lett. 2002; 4: 855
    • 3b Tsuboyama A, Iwawaki H, Furugori M, Mukaide T, Kamatani J, Igawa S, Moriyama T, Miura S, Takiguchi T, Okada S, Hoshino M, Ueno K. J. Am. Chem. Soc. 2003; 125: 12971
    • 3c Fang K.-H, Wu L.-L, Huang Y.-T, Yang C.-H, Sun I.-W. Inorg. Chim. Acta 2006; 359: 441
    • 3d Liu S.-J, Zhao Q, Chen R.-F, Deng Y, Fan Q.-L, Li F.-Y, Wang L.-H, Huang C.-H, Huang W. Chem. Eur. J. 2006; 12: 4351
    • 3e Zhao Q, Liu S, Shi M, Wang C, Yu M, Li L, Li F, Yi T, Huang C. Inorg. Chem. 2006; 45: 6152
    • 3f Shin I.-S, Kim JI, Kwon T.-H, Hong J.-I, Lee J.-K, Kim H. J. Phys. Chem. C 2007; 111: 2280
    • 3g Park GY, Kim Y, Ha Y. Mol. Cryst. Liq. Cryst. 2007; 462: 179
    • 3h Ho C.-L, Wong W.-Y, Gao Z.-Q, Chen C.-H, Cheah K.-W, Yao B, Xie Z, Wang Q, Ma D, Wang L, Yu X.-M, Kwok H.-S, Lin Z. Adv. Funct. Mater. 2008; 18: 319
    • 4a Alcock NW, Brown JM, Hulmes GI. Tetrahedron: Asymmetry 1993; 4: 743
    • 4b Lim CW, Tissot O, Mattison A, Hooper MW, Brown JM, Cowley AR, Hulmes DI, Blacker AJ. Org. Process Res. Dev. 2003; 7: 379
    • 4c Sweetman BA, Muller-Bunz H, Guiry PJ. Tetrahedron Lett. 2005; 46: 4643
    • 4d Durola F, Sauvage J.-P, Wenger OS. Chem. Commun. 2006; 171
    • 5a Bischler A, Napieralski B. Ber. Dtsch. Chem. Ges. 1893; 26: 1903
    • 5b Pomeranz C. Monatsh. Chem. 1893; 14: 116
    • 5c Fritsch P. Ber. Dtsch. Chem. Ges. 1893; 26: 419
    • 5d Pictet A, Spengler T. Ber. Dtsch. Chem. Ges. 1911; 44: 2030

      For some selected reviews on transition-metal-catalyzed C–H functionalization, see:
    • 6a Shilov AE, Shul’pin GB. Chem. Rev. 1997; 97: 2879
    • 6b Alberico D, Scott ME, Lautens M. Chem. Rev. 2007; 107: 174
    • 6c Lyons TW, Sanford MS. Chem. Rev. 2010; 110: 1147
    • 6d Colby DA, Bergman RG, Ellman JA. Chem. Rev. 2010; 110: 624
    • 6e Ackermann L. Chem. Rev. 2011; 111: 1315
    • 6f Engle KM, Mei T.-S, Wasa M, Yu J.-Q. Acc. Chem. Res. 2012; 45: 788
    • 6g Arockiam PB, Bruneau C, Dixneuf PH. Chem. Rev. 2012; 112: 5879
    • 6h Hickman AJ, Sanford MS. Nature 2012; 484: 177
    • 6i Ros A, Fernandez R, Lassaletta JM. Chem. Soc. Rev. 2014; 43: 3229
    • 6j Ackermann L. Acc. Chem. Res. 2014; 47: 281
    • 6k Daugulis O, Roane J, Tran LD. Acc. Chem. Res. 2015; 48: 1053
    • 6l Chen Z, Wang B, Zhang J, Yu W, Liu Z, Zhang Y. Org. Chem. Front. 2015; 2: 1107
    • 6m Das R, Kumar GS, Kapur M. Eur. J. Org. Chem. 2017; 5439
    • 6n Das R, Kapur M. Asian J. Org. Chem. 2018; 7: 1217
    • 6o Tiwari VK, Kapur M. Org. Biomol. Chem. 2019; 17: 1007
    • 7a Lim S.-G, Lee JH, Moon CW, Hong J.-B, Jun C.-H. Org. Lett. 2003; 5: 2759
    • 7b Colby DA, Bergman RG, Ellman JA. J. Am. Chem. Soc. 2008; 130: 3645
    • 7c Guimond N, Fagnou K. J. Am. Chem. Soc. 2009; 131: 12050
    • 7d Chinnagolla RK, Pimparkar S, Jeganmohan M. Org. Lett. 2012; 14: 3032
    • 7e Chuang S.-C, Gandeepan P, Cheng C.-H. Org. Lett. 2013; 15: 5750
    • 7f Huang X.-C, Yang X.-H, Song R.-J, Li J.-H. J. Org. Chem. 2014; 79: 1025
    • 7g Han W, Zhang G, Li G, Huang H. Org. Lett. 2014; 16: 3532
    • 7h Muralirajan K, Kuppusamy R, Prakash S, Cheng C.-H. Adv. Synth. Catal. 2016; 358: 774
    • 8a Zhu Z, Tang X, Li X, Wu W, Deng G, Jiang H. J. Org. Chem. 2016; 81: 1401
    • 8b Li J, Zhang Z, Tang M, Zhang X, Jin J. Org. Lett. 2016; 18: 3898
    • 8c Zhou Q, Zhang Z, Zhou Y, Li S, Zhang Y, Wang J. J. Org. Chem. 2017; 82: 48
    • 8d Feng R, Ning H, Su H, Gao Y, Yin H, Wang Y, Yang Z, Qi C. J. Org. Chem. 2017; 82: 10408
    • 9a Rouchet J.-BE. Y, Schneider C, Fruit C, Hoarau C. J. Org. Chem. 2015; 80: 5919
    • 9b Guo T, Liu Y, Zhao Y.-H, Zhang P.-K, Han S.-L, Liu H.-M. Tetrahedron Lett. 2016; 57: 3920
    • 10a Tiwari VK, Pawar GG, Jena HS, Kapur M. Chem. Commun. 2014; 50: 7322
    • 10b Tiwari VK, Kamal N, Kapur M. Org. Lett. 2017; 19: 262

      For two indirect methods, see:
    • 11a Goriya Y, Ramana CV. Chem. Eur. J. 2012; 18: 13288
    • 11b Song G, Wang B, Nishiura M, Hou Z. Chem. Eur. J. 2015; 21: 8394
  • 12 CCDC 1590567 (3j) contains the supplementary crystallographic data for this paper. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.