Catalytic Enantioselective
Friedel-Crafts Alkylation of Indoles with β,γ-Unsaturated α-Keto
Phosphonates in the Presence of Chiral Palladium Complexes

Young Ku Kang; Ki Hyung Suh; Dae Young Kim

doi:10.1055/s-0030-1259932

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Synlett 2011(8): 1125-1128
DOI: 10.1055/s-0030-1259932

LETTER

Catalytic Enantioselective Friedel-Crafts Alkylation of Indoles with β,γ-Unsaturated α-Keto Phosphonates in the Presence of Chiral Palladium Complexes

Young Ku Kang, Ki Hyung Suh, Dae Young Kim*
Department of Chemistry, Soonchunhyang University, Asan, Chungnam 336-745, Korea
Fax: +82(41)5301247; e-Mail: dyoung@sch.ac.kr;

Further Information

Publication History

Received 18 February 2011
Publication Date:
30 March 2011 (online)

Abstract
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Abstract

The catalytic enantioselective Friedel-Crafts alkylation reaction promoted by chiral palladium complexes is described. The treatment of indoles with β,γ-unsaturated α-keto phosphonates under the mild reaction conditions afforded the corresponding Friedel-Crafts alkylation adducts with excellent enantioselectivities (up to 99% ee).

Key words

Friedel-Crafts reaction - asymmetric catalysis - chiral palladium catalysts - indoles - β,γ-unsaturated α-keto phosphonates

References and Notes

For reviews on Friedel-Crafts Alkylation, see:
1a Jørgensen KA. Synthesis 2003, 1117

Google Scholar
1b Bandini M. Melloni A. Umani-Ronchi A. Angew. Chem. Int. Ed. 2004, 43: 550

Google Scholar
1c Bandini M. Melloni A. Tommasi S. Umani-Ronchi A. Synlett 2005, 1199

Google Scholar
1d Poulsen TB. Jørgensen KA. Chem. Rev. 2008, 108: 2903

Google Scholar
1e Tsogoeva SB. Eur. J. Org. Chem. 2007, 1701

Google Scholar
1f You S.-L. Cai Q. Zeng M. Chem. Soc. Rev. 2009, 38: 210

Google Scholar
1g Bandini M. Umani-Ronchi A. Catalytic Asymmetric Friedel-Crafts Alkylations Wiley-VCH; Weinheim: 2009.

Google Scholar
1h Zeng M. You S.-L. Synlett 2010, 1289

Google Scholar
1i Terrasson V. de Figueiredo RM. Campagne JM. Eur. J. Org. Chem. 2010, 2635

Google Scholar
2a Sundberg RJ. Indoles Academic Press; San Diego: 1996.

Google Scholar
2b Toyota M. Ihara M. Nat. Prod. Rep. 1998, 15: 327

Google Scholar
2c Huber U. Moore RE. Patterson GML. J. Nat. Prod. 1998, 61: 1304

Google Scholar
2d Kinsman AC. Kerr MA.
J. Am. Chem. Soc. 2003, 125: 14120

Google Scholar
2e Mancini I. Guella G. Zibrowius H. Pietra F. Tetrahedron 2003, 59: 8757

Google Scholar
2f Kam T.-S. Choo Y.-M. J. Nat. Prod. 2004, 67: 547

Google Scholar
3a Somei M. Yamada F. Nat. Prod. Rep. 2005, 22: 73

Google Scholar
3b Reddy R. Jaquith JB. Neelagiri VR. Saleh-Hanna S. Durst T. Org. Lett. 2002, 4: 695

Google Scholar
3c King HD. Meng Z. Denhart D. Mattson R. Kimura R. Wu D. Gao Q. Macor JE. Org. Lett. 2005, 7: 3437

Google Scholar
3d Baran PS. Richter JM. J. Am. Chem. Soc. 2004, 126: 7450

Google Scholar
4a Lv J. Li X. Zhong L. Luo S. Cheng J.-P. Org. Lett. 2010, 12: 1096

Google Scholar
4b Liu Y. Shang D. Zhou X. Zhu Y. Lin L. Liu X. Feng X. Org. Lett. 2010, 12: 180

Google Scholar
4c Singh PK. Singh VK. Org. Lett. 2008, 10: 4121

Google Scholar
4d Yang H. Hong Y.-T. Kim S. Org. Lett. 2007, 9: 2281

Google Scholar
4e Blay G. Fernandez I. Pedro JR. Vila C. Org. Lett. 2007, 9: 2601

Google Scholar
4f Evans DA. Fandrick KR. Song H.-J. J. Am. Chem. Soc. 2005, 127: 8942

Google Scholar
4g Yamazaki S. Iwata Y. J. Org. Chem. 2006, 71: 739

Google Scholar
4h Palomo C. Oiarbide M. Kardak BG. Garcia JM. Linden A. J. Am. Chem. Soc. 2005, 127: 4154

Google Scholar
4i Bandini M. Fagioli M. Melchiorre P. Melloni A. Umani-Ronchi A. Tetrahedron Lett. 2003, 44: 5843

Google Scholar
4j Bandini M. Melloni A. Tommasi S. Umani-Ronchi A. Helv. Chim. Acta 2003, 86: 3753

Google Scholar
5a Evans DA. Scheidt KA. Fandrick KR. Lam HW. Wu J. J. Am. Chem. Soc. 2003, 125: 10780

Google Scholar
5b Evans DA. Fandrick KR. Song H.-J. Scheidt KA. Xu R. J. Am. Chem. Soc. 2007, 129: 10029

Google Scholar
6 Takenaka N. Abell JP. Yamamoto H. J. Am. Chem. Soc. 2007, 129: 742

Crossref Google Scholar
7a Shi Z.-H. Sheng H. Yang K.-F. Jiang J.-X. Lai G.-Q. Lu Y. Xu L.-W. Eur. J. Org. Chem. 2011, 66

Google Scholar
7b Jiang H. Paixoã MW. Monge D. Jørgensen KA.
J. Am. Chem. Soc. 2010, 132: 2775

Google Scholar
7c Bachu P. Akiyama T. Chem. Commun. 2010, 46: 4112

Google Scholar
7d Cai C. Zhao Z.-A. You S.-L. Angew. Chem. Int. Ed. 2009, 48: 7428

Google Scholar
7e Sheng Y.-F. Gu Q. Zhang A.-J. You S.-L. J. Org. Chem. 2009, 74: 6899

Google Scholar
7f Tang H.-Y. Lu A.-D. Zhou Z.-H. Zhao G.-F. He L.-N. Tang C.-C. Eur. J. Org. Chem. 2008, 1406

Google Scholar
7g Bartoli G. Melchiorre P. Synlett 2008, 1759

Google Scholar
7h Rueping M. Nachtsheim BJ. Moreth SA. Bolte M. Angew. Chem. Int. Ed. 2008, 47: 593

Google Scholar
7i Nakamura S. Hyodo K. Nakamura Y. Shibata N. Toru T. Adv. Synth. Catal. 2008, 350: 1443

Google Scholar
7j Li C.-F. Liu H. Liao J. Cao Y.-J. Liu X.-P. Xiao W.-J. Org. Lett. 2007, 9: 1847

Google Scholar
7k Chen W. Du W. Yue L. Li R. Wu Y. Ding L.-S. Chen Y.-C. Org. Biomol. Chem. 2007, 5: 816

Google Scholar
7l Bartoli G. Bosco M. Carlone A. Pesciaioli F. Sambri L. Melchiorre P. Org. Lett. 2007, 9: 1403

Google Scholar
7m Li H. Wang Y.-Q. Deng L. Org. Lett. 2006, 8: 4063

Google Scholar
7n Török B. Abid M. London G. Esquibel J. Török M. Mhadgut SC. Yan P. Prakash GKS. Angew.Chem. Int. Ed. 2005, 44: 3086

Google Scholar
7o Austin JF. MacMillan DWC. J. Am. Chem. Soc. 2002, 124: 1172

Google Scholar
For recent selected examples of the enantioselective reactions catalyzed by chiral palladium complexes, see:
8a Lectard S. Hamashima Y. Sodeoka M. Adv. Synth. Catal. 2010, 352: 2708

Google Scholar
8b Sodeoka M. Hamashima Y. Chem. Commun. 2009, 5787

Google Scholar
8c Hamashima Y. Sasamoto N. Umebayashi N. Sodeoka M. Chem. Asian J. 2008, 3: 1443

Google Scholar
8d Hamashima Y. Sasamoto N. Hotta D. Somei H. Umebayashi N. Sodeoka M. Angew. Chem. Int. Ed. 2005, 44: 1525

Google Scholar
8e Smith AMR. Rzepa HS. White AJP. Billen D. Hii KK. J. Org. Chem. 2010, 75: 3085

Google Scholar
8f Smith AMR. Billen D. Hii KK. Chem. Commun. 2009, 3925

Google Scholar
8g Phua PH. Mathew SP. White AJP. de Vries JG. Blackmond DG. Hii KK. Chem. Eur. J. 2007, 13: 4602

Google Scholar
9a Yoon SJ. Kang YK. Kim DY. Synlett 2011, 420

Google Scholar
9b Moon HW. Kim DY. Bull. Korean Chem. Soc. 2011, 32: 291

Google Scholar
9c Kang YK. Kim SM. Kim DY. J. Am. Chem. Soc. 2010, 132: 11847

Google Scholar
9d Kang SH. Kim DY. Adv. Synth. Catal. 2010, 352: 2783

Google Scholar
9e Lee JH. Kim DY. Synthesis 2010, 1860

Google Scholar
9f Moon HW. Kim DY. Tetrahedron Lett. 2010, 51: 2906

Google Scholar
9g Lee JH. Kim DY. Adv. Synth Catal. 2009, 351: 1779

Google Scholar
9h Kang YK. Kim DY. J. Org. Chem. 2009, 74: 5734

Google Scholar
9i Moon HW. Cho MJ. Kim DY. Tetrahedron Lett. 2009, 50: 4896

Google Scholar
9j Kwon BK. Kim SM. Kim DY. J. Fluorine Chem. 2009, 130: 259

Google Scholar
9k Oh Y. Kim SM. Kim DY. Tetrahedron Lett. 2009, 50: 4674

Google Scholar
9l Kang SH. Kim DY. Bull. Korean Chem. Soc. 2009, 30: 1439

Google Scholar
9m Kwon BK. Kim DY. Bull. Korean Chem. Soc. 2009, 30: 1441

Google Scholar
9n Mang JY. Kwon DG. Kim DY. Bull. Korean Chem. Soc. 2009, 30: 249

Google Scholar
9o Kim SM. Lee JH. Kim DY. Synlett 2008, 2659

Google Scholar
9p Jung SH. Kim DY. Tetrahedron Lett. 2008, 49: 5527

Google Scholar
9q Park EJ. Kim MH. Kim DY. J. Org. Chem. 2004, 69: 6897

Google Scholar
9r Kim DY. Choi YJ. Park HY. Joung CU. Koh KO. Mang JY. Jung K.-Y. Synth. Commun. 2003, 33: 435

Google Scholar
9s Kim DY. Park EJ. Org. Lett. 2002, 4: 545

Google Scholar
9t Kim DY. Huh SC. Kim SM. Tetrahedron Lett. 2001, 42: 6299

Google Scholar
9u Kim DY. Huh SC. Tetrahedron 2001, 57: 8933

Google Scholar
10a Kang SH. Kang YK. Kim DY. Tetrahedron 2009, 65: 5676

Google Scholar
10b Kim EJ. Kang YK. Kim DY. Bull. Korean Chem. Soc. 2009, 30: 1437

Google Scholar
10c Lee NR. Kim SM. Kim DY. Bull. Korean Chem. Soc. 2009, 30: 829

Google Scholar
10d Kang YK. Kim DY. Bull. Korean Chem. Soc. 2008, 29: 2093

Google Scholar
10e Lee JH. Bang HT. Kim DY. Synlett 2008, 1821

Google Scholar
10f Kang YK. Cho MJ. Kim SM. Kim DY. Synlett 2007, 1135

Google Scholar
10g Cho MJ. Kang YK. Lee NR. Kim DY. Bull. Korean Chem. Soc. 2007, 28: 2191

Google Scholar
10h Kim SM. Kang YK. Cho MJ. Kim DY. Bull. Korean Chem. Soc. 2007, 28: 2435

Google Scholar
10i Cho MJ. Kang YK. Lee NR. Kim DY. Bull. Korean Chem. Soc. 2007, 28: 2191

Google Scholar
10j Kim SM. Kang YK. Lee K. Mang JY. Kim DY. Bull. Korean Chem. Soc. 2006, 27: 423

Google Scholar
10k Kang YK. Kim DY. Tetrahedron Lett. 2006, 47: 4265

Google Scholar
10l Kim HR. Kim DY. Tetrahedron Lett. 2005, 46: 3115

Google Scholar
10m Kim SM. Kim HR. Kim DY. Org. Lett. 2005, 7: 2309

Google Scholar

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Typical Procedure
To a stirred solution of (E)-diethyl 1-oxobut-2-enylphos-phonate (2a, 20.6 mg, 0.1 mmol), Pd catalyst 1c (5.4 mg, 0.005 mmol) in CH₂Cl₂ (1 mL) was added indole (3a, 14.0 mg, 0.12 mmol) at r.t. The reaction mixture was stirred for 2 h at r.t. Then MeOH (0.15 mL), followed by DBU (0.03 mL), was added directly to the reaction mixture. The reaction was allowed to stir for 2 h at r.t. The reaction was diluted with EtOAc (10 mL), then washed with sat. NH₄Cl. The organic layer was dried over anhyd MgSO₄, filtered, concentrated, and purified by flash column chromatography (EtOAc-hexane, 1:5) to afford (S)-methyl 3-(1H-indol-3-yl)butanoate (4a, 70%, 15.2 mg). [α]_D ^²8 7.3 (c 0.7, CHCl₃, 93% ee). ^¹H NMR (200 MHz, CDCl₃): δ = 7.99 (br s, 1 H), 7.63 (d, J = 7.8 Hz, 1 H), 7.28 (d, J = 7.6 Hz, 1 H), 7.23-7.05 (m, 2 H), 6.90 (d, J = 2.5 Hz, 1 H), 3.65-3.47 (m, 1 H), 3.62 (s, 3 H), 2.82 (dd, J = 14.8, 6.0 Hz, 1 H), 2.56 (dd, J = 14.7, 8.7 Hz, 1 H), 1.39 (d, J = 6.9 Hz, 3 H). ^¹³C NMR (50 MHz, CDCl₃): δ = 173.0, 136.1, 125.9, 121.5, 120.2, 119.7, 118.8, 118.7, 110.9, 51.1, 41.9, 27.6, 20.6. ESI-MS: m/z = 217.9 [M + H]⁺, 117.0, 120.9, 123.0 147.0, 176.9. HPLC (hexane-i-PrOH = 90:10, 220 nm, 0.8 mL/min) Chiralcel OD-H column, t _R = 9.0 min(minor), t _R = 13.8 (major).

12

The two-site-binding interaction between substrate and palladium catalyst is crucial to guarantee reactivity as well as stereocontrol. In fact, when the monodentate ethyl (E)-but-2-enoate was reacted with indole under the same reaction conditions, no reaction occurred.