Annulation of Indoles with 1,n-Dibromoalkanes by a Pd(II)-Catalyzed and Norbornene-Mediated Reaction Cascade

Michael Henkel; Thorsten Bach

doi:10.1055/s-0039-1690693

Synthesis, Table of Contents

Synthesis 2020; 52(08): 1231-1238
DOI: 10.1055/s-0039-1690693

special topic

Annulation of Indoles with 1,n-Dibromoalkanes by a Pd(II)-Catalyzed and Norbornene-Mediated Reaction Cascade

Michael Henkel

,

Thorsten Bach ∗

Abstract

All articles of this category

Dedicated to Professor Mark Lautens on the occasion of his 60^th birthday

Published as part of the Special Topic Domino C–H Functionalization Reaction/Cascade Catalysis

Abstract

Employing 1,3-dibromopropane, 1,4-dibromobutane, and 1,5-dibromopentane as biselectrophiles, the annulation of indoles was probed in the presence of PdCl₂(MeCN)₂ as a catalyst and norbornene as a transpositional ligand. Ring formation to a five-membered ring was observed at positions C2 and N, while annulation of a six-membered ring occurred at positions C2 and C3. The latter cascade process was successfully applied to the direct synthesis of 1,2,3,4-tetrahydrocarbazoles from indoles (11 examples, 31–68% yield). Seven-membered-ring annulation was feasible by an initial coupling at positon C2 followed by alkylation at C3.

Key words

alkylation - C–H activation - domino reaction - indoles - Pd catalysis

Full Text

References

References

Selected reviews and monographs:

1a Sundberg RJ. Indoles . Academic Press; San Diego: 1996
1b Joule JA. In Science of Synthesis, Vol. 10. Thomas EJ. Thieme; Stuttgart: 2000: 361-652
1c Gribble GW. J. Chem. Soc., Perkin Trans. 1 2000; 1045
1d Tois J, Franzén R, Koskinen A. Tetrahedron 2003; 59: 5395
1e Platon M, Amardeil R, Djakovitch L, Hierso J.-C. Chem. Soc. Rev. 2012; 41: 3929
1f Inman M, Moody CJ. Chem. Sci. 2013; 4: 29
1g Gribble GW. Indole Ring Synthesis: From Natural Products to Drug Discovery. Wiley; Chichester: 2016
1h Mancuso R, Dalpozzo R. Catalysts 2018; 8: 458

Selected reviews:

2a Cacchi S, Fabrizi G. Chem. Rev. 2005; 105: 2873
2b Seregin IV, Gevorgyan V. Chem. Soc. Rev. 2007; 36: 1173
2c Bandini M, Eichholzer A. Angew. Chem. Int. Ed. 2009; 48: 9608
2d Bartoli G, Bencivenni G, Dalpozzo R. Chem. Soc. Rev. 2010; 39: 4449
2e Lebrasseur N, Larrosa I. Adv. Heterocycl. Chem. 2012; 105: 309
2f Dalpozzo R. Chem. Soc. Rev. 2015; 44: 742
2g Leitch JA, Bhonoah Y, Frost CG. ACS Catal. 2017; 7: 5618
2h Vorobyeva DV, Osipov SN. Synthesis 2018; 50: 227
2i Kalepu J, Gandeepan P, Ackermann L, Pilarski LT. Chem. Sci. 2018; 9: 4203
2j Sandtorv AH. Adv. Synth. Catal. 2018; 357: 2403
2k Le Bras J, Muzart J. Synthesis 2019; 51: 2871

Reviews:

3a Ye J, Lautens M. Nat. Chem. 2015; 7: 863
3b Della Ca’ N, Fontana M, Motti E, Catellani M. Acc. Chem. Res. 2016; 49: 1389
3c Wang J, Dong G. Chem. Rev. 2019; 119: 7478

4a Jiao L, Bach T. J. Am. Chem. Soc. 2011; 133: 12990
4b Jiao L, Herdtweck E, Bach T. J. Am. Chem. Soc. 2012; 134: 14563
4c Potukuchi HK, Bach T. J. Org. Chem. 2013; 78: 12263
4d Jiao L, Bach T. Synthesis 2014; 46: 35

5 Recent review: Wegmann M, Henkel M, Bach T. Org. Biomol. Chem. 2018; 16: 5376

Recent reviews:

6a Haak E. Synlett 2019; 30: 245
6b Ciulla MG, Zimmermann S, Kumar K. Org. Biomol. Chem. 2019; 17: 413

7a Jeffery T. J. Chem. Soc., Chem. Commun. 1984; 1287
7b Jeffery T. Tetrahedron Lett. 1985; 26: 2667

8 Synthesis of [a]-indole derivatives by the cyclization method: Jiang C, Gao Y, Li J. CN 108003160, 2018
9 Ishikura M, Terashima M. Tetrahedron Lett. 1992; 33: 6849

10a Wender PA, Cooper CB. Tetrahedron 1986; 42: 2985
10b Chen HG, Hoechstetter C, Knochel P. Tetrahedron Lett. 1989; 30: 4795

11 Review: Monakhova N, Ryabova S, Makarov V. J. Heterocycl. Chem. 2016; 53: 685

12a Ziegler FE, Jeroncic LO. J. Org. Chem. 1991; 56: 3479
12b Artis DR, Cho I.-S, Jaime-Figueroa S, Muchowski JM. J. Org. Chem. 1994; 59: 2456
12c Caddick S, Aboutayab K, Jenkins K, West RI. J. Chem. Soc., Perkin Trans. 1 1996; 675
12d Venning AR. O, Bohan PT, Alexanian EJ. J. Am. Chem. Soc. 2015; 137: 3731
12e Kaldas SJ, Cannillo A, McCallum T, Barriault L. Org. Lett. 2015; 17: 2864

13a Noland WE, Xia G.-M, Gee KR, Konkel MJ, Whalstrom MJ, Condoluci JJ, Rieger DL. Tetrahedron 1996; 52: 4555
13b Youn SW, Pastine SJ, Sames D. Org. Lett. 2004; 6: 581
13c Loh CC. J, Raabe G, Enders D. Chem. Eur. J. 2012; 18: 13250
13d Wu Y, Peng X, Luo B, Wu F, Liu B, Song F, Huang P, Wen S. Org. Biomol. Chem. 2014; 12: 9777
13e El-Sayed MT, Mahmoud KA, Heinemann FW, Hilgeroth A. J. Heterocycl. Chem. 2017; 54: 714
13f Hansen CL, Ohm RG, Olsen LB, Ascic E, Tanner D, Nielsen TE. Org. Lett. 2016; 18: 5990
13g Chen S, Li Y, Ni P, Yang B, Huang H, Deng G.-J. J. Org. Chem. 2017; 82: 2935
13h Garayalde D, Rusconi G, Nevado C. Helv. Chim. Acta 2017; 100: e1600333
13i Wang W, Bai X, Jin S, Guo J, Zhao Y, Miao H, Zhu Y, Wang Q, Bu Z. Org. Lett. 2018; 20: 3451
13j Kaufmann J, Jäckel E, Haak E. Angew. Chem. Int. Ed. 2018; 57: 5908
13k Yang R.-Y, Sun J, Sun Q, Yan C.-G. J. Org. Chem. 2018; 83: 5909
13l Liu B, Li J, Hu P, Zhou X, Bai D, Li X. ACS Catal. 2018; 8: 9463

14 While our work was in progress a patent entitled ‘Method for synthesizing [b]-cyclized indole derivatives’ appeared in which some closely related annulation reactions (Table 1, entries 1–3) were disclosed: Jiang C, Li J, Gao Y. CN 108084082, 2018

15a Rice LM, Hertz E, Freed ME. J. Med. Chem. 1964; 7: 313
15b Robarge MJ, Bom DC, Tumey LN, Varga N, Gleason E, Silver D, Song J, Murphy SM, Ekema G, Doucette C, Hanniford D, Palmer M, Pawlowski G, Danzig J, Loftus M, Hunady K, Sherf BA, Mays RW, Stricker-Krongrad A, Brunden KR, Harrington JJ, Bennani YL. Bioorg. Med. Chem. Lett. 2005; 15: 1749

16 For a related cyclization, see: Wong CM, Vuong KQ, Gatus MR. D, Hua C, Bhadbhade M, Messerle BA. Organometallics 2012; 31: 7500
17 Review: Stempel E, Gaich T. Acc. Chem. Res. 2016; 49: 2390

18a Nguyen Q, Nguyen T, Driver TG. J. Am. Chem. Soc. 2013; 135: 620
18b Tong S, Xu Z, Mamboury M, Wang Q, Zhu J. Angew. Chem. Int. Ed. 2015; 54: 11809

19 Clark RD, Muchowski JM, Fischer LE, Flippin LA, Repke DB, Souchet M. Synthesis 1991; 871
20 Recent review: Evano G, Theunissen C. Angew. Chem. Int. Ed. 2019; 58: 7558
21 Brice JL, Harang JE, Timokhin VI, Anastasi NR, Stahl SS. J. Am. Chem. Soc. 2005; 127: 2868
22 For a recent review on norbornene in organic synthesis, see: Li C, Liu L, Fu X, Huang J. Synthesis 2018; 50: 2799
23 Baldwin JE, Kruse LI. J. Chem. Soc., Chem. Commun. 1977; 233
24 Tsotinis A, Pandelis AA, Davidson K, Prashar A, Sugden D. J. Med. Chem. 2007; 50: 6436
25 Xu D.-Q, Wu J, Luo S.-P, Zhang J.-X, Wu J.-Y, Du X.-H, Xu Z.-Y. Green Chem. 2009; 11: 1239
26 Haag BA, Zhang Z.-G, Li J.-S, Knochel P. Angew. Chem. Int. Ed. 2010; 49: 9513
27 Lin Y, Ye J, Zhang W, Gao Y, Chen H. Adv. Synth. Catal. 2019; 361: 432
28 Novel heteroaryl-substituted acetone derivatives as inhibitors of phospholipase A2: Lehr M, Ludwig J. WO 2004069797, 2004

Supplementary Material

Supporting Information

Primary Data

Primary Data