Iridium-Catalyzed C-3 Allylation of Indoles with Allylic Alcohols Promoted by a Brønsted Acid

Shu-jie Chen; Guo-ping Lu; Chun Cai

doi:10.1055/s-0033-1341156

Synthesis, Table of Contents

Synthesis 2014; 46(13): 1717-1724
DOI: 10.1055/s-0033-1341156

paper

Iridium-Catalyzed C-3 Allylation of Indoles with Allylic Alcohols Promoted by a Brønsted Acid

Shu-jie Chen

Chemical Engineering College, Nanjing University of Science & Technology, Nanjing, Jiangsu 210094, P. R. of China Email: c.cai@mail.njust.edu.cn Fax: +86(25)84315030

,

Guo-ping Lu

Chemical Engineering College, Nanjing University of Science & Technology, Nanjing, Jiangsu 210094, P. R. of China Email: c.cai@mail.njust.edu.cn Fax: +86(25)84315030

,

Chun Cai*

Chemical Engineering College, Nanjing University of Science & Technology, Nanjing, Jiangsu 210094, P. R. of China Email: c.cai@mail.njust.edu.cn Fax: +86(25)84315030

› Author Affiliations

Abstract

All articles of this category

Abstract

A highly regioselective method has been developed for the allylation of indoles with an iridium catalyst. This regioselective procedure uses allylic alcohols directly as allylating agents in the presence of a catalytic amount of sulfuric acid. A wide range of indoles reacted smoothly with asymmetrical allylic alcohols to give the corresponding branched products in branched-to-linear ratios of up to 99:1 and yields as high as 92%. A series of inorganic and organic acids were tested in this approach, and it was shown that acids with pK _a values in acetonitrile of less than 15 are required in this iridium-catalyzed system.

Key words

iridium - allylations - indoles - regioselectivity - homogeneous catalysis

Full Text

References

References

For reviews, see:

1a Saxton JE. Nat. Prod. Rep. 1997; 14: 559
1b Faulkner DJ. Nat. Prod. Rep. 2002; 19: 1
1c Kawasaki T, Higuchi K. Nat. Prod. Rep. 2005; 22: 761
1d O’Connor SE, Maresh JJ. Nat. Prod. Rep. 2006; 23: 532

2 Pollmann S, Düchting P, Weiler EW. Phytochemistry 2009; 70: 523
3 Carbone C, Musumeci T, Pignatello R In Drug–Biomembrane Interaction Studies: The Application of Calorimetric Techniques . Pignatello R. Woodhead; Cambridge: 2013. Chap. 9, 281

For select reviews, see:

4a Cacchi S, Fabrizi G. Chem. Rev. 2005; 105: 2873
4b Joucla L, Djakovitch L. Adv. Synth. Catal. 2009; 351: 673
4c Bartoli G, Bencivenni G, Dalpozzo R. Chem. Soc. Rev. 2010; 39: 4449
4d Cacchi S, Fabrizi G. Chem. Rev. 2011; 111: PR215

For select examples, see:

5a Brow JB, Henbest HB, Jones ER. H. J. Chem. Soc. 1952; 3172
5b Chen Y.-K, Chung H.-F, Sheu J.-H. Nat. Prod. Lett. 1994; 5: 225
5c Bodwell GJ, Li J. Org. Lett. 2002; 4: 127
5d Chiba S, Wang Y.-F, Zhang F.-L. Synthesis 2012; 44: 1526

6 Malkov AV, Davis SL, Baxendale IR, Mitchell WL, Kočovský P. J. Org. Chem. 1999; 64: 2751

7a Bandini M, Melloni A, Umani-Ronchi A. Org. Lett. 2004; 6: 3199
7b Bandini M, Melloni A, Piccinelli F, Sinisi R, Tommasi S, Umani-Ronchi A. J. Am. Chem. Soc. 2006; 128: 1424
7c Cheung HY, Yu W.-Y, Lam FL, Au-Yeung TT.-L, Zhou Z, Chan TH, Chan AS. C. Org. Lett. 2007; 9: 4295
7d Wu Q.-F, He H, Liu W.-B, You S.-L. J. Am. Chem. Soc. 2010; 132: 11418
7e Cao Z, Liu Y, Liu Z, Feng X, Zhuang M, Du H. Org. Lett. 2011; 13: 2164
7f Hoshi T, Sasaki K, Sato S, Ishii Y, Suzuki T, Hagiwara H. Org. Lett. 2011; 13: 932
7g Wu Q.-F, Zheng C, You S.-L. Angew. Chem. Int. Ed. 2012; 51: 1680
7h Liu Y, Du H. Org. Lett. 2013; 15: 740

8 Kimura M, Futamata M, Mukai R, Tamaru Y. J. Am. Chem. Soc. 2005; 127: 4592

9a Zaitsev AB, Gruber S, Pregosin PS. Chem. Commun. 2007; 4692
9b Gruber S, Zaitsev AB, Wörle M, Pregosin PS, Veiros LF. Organometallics 2008; 27: 3796
9c Zaitsev AB, Gruber S, Pluss PA, Pregosin PS, Veiros LF, Wörle M. J. Am. Chem. Soc. 2008; 130: 11604
9d Gruber S, Zaitsev AB, Wörle M, Pregosin PS, Veiros LF. Organometallics 2009; 28: 3437

10a Bandini M, Eichholzer A. Angew. Chem. Int. Ed. 2009; 48: 9533
10b Bandini M, Eichholzer A, Gualandi A, Quinto T, Savoia D. ChemCatChem 2010; 2: 661
10c Bandini M, Gualandi A, Monari M, Romaniello A, Savoia D, Tragni M. J. Organomet. Chem. 2011; 696: 338
10d Bandini M, Bottoni A, Chiarucci M, Cera G, Miscione GP. J. Am. Chem. Soc. 2012; 134: 20690

For selected reviews, see:

10e Biannic B, Aponick A. Eur. J. Org. Chem. 2011; 6605
10f Bandini M, Cera G, Chiarucci M. Synthesis 2012; 44: 504

11 Zhang X, Yang Z.-P, Liu C, You S.-L. Chem. Sci. 2013; 4: 3239

For other select examples, see:

12a Bandini M, Tragni M. Org. Biomol. Chem. 2009; 7: 1501
12b Trost BM, Quancard J. J. Am. Chem. Soc. 2006; 128: 6314
12c Usui I, Schmidt S, Keller M, Breit B. Org. Lett. 2008; 10: 1207
12d Sundararaju B, Achard M, Demerseman B, Toupet L, Sharma GV, Bruneau C. Angew. Chem. Int. Ed. 2010; 49: 2782

13 Liu W.-B, He H, Dai L.-X, You S.-L. Org. Lett. 2008; 10: 1815
14 Tao Y, Wang B, Zhao J, Song Y, Qu L, Qu J. J. Org. Chem. 2012; 77: 2942
15 Zhang X, Han L, You S.-L. Chem. Sci. 2013; 5: 1059

16a Defieber C, Ariger MA, Moriel P, Carreira EM. Angew. Chem. Int. Ed. 2007; 46: 3139
16b Roggen M, Carreira EM. Angew. Chem. Int. Ed. 2011; 50: 5568
16c Roggen M, Carreira EM. Angew. Chem. Int. Ed. 2012; 51: 8652
16d Lafrance M, Roggen M, Carreira EM. Angew. Chem. Int. Ed. 2012; 51: 3470
16e Krautwald S, Sarlah D, Schafroth MA, Carreira EM. Science 2013; 340: 1065
16f Hamilton JY, Sarlah D, Carreira EM. J. Am. Chem. Soc. 2013; 135: 994
16g Hamilton JY, Sarlah D, Carreira EM. Angew. Chem. Int. Ed. 2013; 52: 7532

17 Eckert F, Leito I, Kaljurand I, Kütt A, Klamt A, Diedenhofen M. J. Comput. Chem. 2009; 30: 799
18 Logan AW, Parker JS, Hallside MS, Burton JW. Org. Lett. 2012; 14: 2940
19 Zhang Y, Stephens D, Hernandez G, Mendoza R, Larionov OV. Chem. Eur. J. 2012; 18: 16612

Supplementary Material

Supporting Information