Enantioselective Rauhut–Currier-Type Cyclizations via Dienamine Activation: Scope and Mechanism

Eugenia Marqués-López; Raquel P. Herrera; Timo Marks; Wiebke C. Jacobs; Mathias Christmann

doi:10.1055/s-0032-1316864

Synthesis, Inhaltsverzeichnis

Synthesis 2013; 45(8): 1016-1028
DOI: 10.1055/s-0032-1316864

feature article

Enantioselective Rauhut–Currier-Type Cyclizations via Dienamine Activation: Scope and Mechanism

Eugenia Marqués-López*

^aTU Dortmund University, Faculty of Chemistry, Otto-Hahn-Straße 6, 44227 Dortmund, Germany Fax: +49(231)7555363 eMail: mathias.christmann@tu-dortmund.de

^bDepartamento de Química Orgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain[1] eMail: mmaamarq@unizar.es

,

Raquel P. Herrera

^aTU Dortmund University, Faculty of Chemistry, Otto-Hahn-Straße 6, 44227 Dortmund, Germany Fax: +49(231)7555363 eMail: mathias.christmann@tu-dortmund.de

^bDepartamento de Química Orgánica, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain[1] eMail: mmaamarq@unizar.es

,

Timo Marks

^aTU Dortmund University, Faculty of Chemistry, Otto-Hahn-Straße 6, 44227 Dortmund, Germany Fax: +49(231)7555363 eMail: mathias.christmann@tu-dortmund.de

,

Wiebke C. Jacobs

^aTU Dortmund University, Faculty of Chemistry, Otto-Hahn-Straße 6, 44227 Dortmund, Germany Fax: +49(231)7555363 eMail: mathias.christmann@tu-dortmund.de

,

Mathias Christmann*

^aTU Dortmund University, Faculty of Chemistry, Otto-Hahn-Straße 6, 44227 Dortmund, Germany Fax: +49(231)7555363 eMail: mathias.christmann@tu-dortmund.de

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

This Feature Article describes our mechanistic studies in organocatalytic Rauhut–Currier-type reactions and some applications in target-oriented synthesis. The developed approach involves the cyclization of two tethered Michael acceptors via dienamine intermediates and leads to highly functionalized cycloalkenes. The utility of these intermediates is further demonstrated by the synthesis of biologically important targets, such as optically active iridoid derivatives.

1 Introduction

2 Organocatalytic Cyclization of Tethered α,β-Unsaturated Carbonyl Compounds; Synthesis of Cyclopentene Derivatives

2.1 Mechanistic Proposal

2.1.1 ESI-HRMS Measurements

2.1.2 NMR Experiments

2.1.3 Complementary Reactivity

2.2 Synthetic Applications

3 Organocatalytic Cyclization of Tethered α,β-Unsaturated Carbonyl Compounds; Synthesis of Cyclohexene Derivatives

4 Conclusions

Key words

asymmetric synthesis - organocatalysis - dienamine activation - Rauhut–Currier reaction - Michael addition - reaction mechanisms

Volltext

Referenzen

References
1 New address for E. Marqués-López and R. P. Herrera.
2 Asymmetric Synthesis: More Methods and Applications. Christmann M, Bräse S. Wiley-VCH; Weinheim: 2012

For selected reviews on organocatalysis, see for example:

3a Dalko PI, Moisan L. Angew. Chem. Int. Ed. 2004; 43: 5138
3b Asymmetric Organocatalysis. Berkessel A, Gröger H. Wiley-VCH; Weinheim: 2004
3c Seayed J, List B. Org. Biomol. Chem. 2005; 3: 719
3d Enantioselective Organocatalysis. Dalko PI. Wiley-VCH; Weinheim: 2007
3e Dondoni A, Massi A. Angew. Chem. Int. Ed. 2008; 47: 4638
3f Buckley BR, Kimber MC, Slater NH. Annu. Rep. Prog. Chem., Sect. B: Org. Chem. 2012; 108: 98
3g Science of Synthesis: Asymmetric Organocatalysis. Vol. 1. List B. Thieme; Stuttgart: 2012
3h Asymmetric Organocatalysis: Science of Synthesis. Vol. 2. Maruoka K. Thieme; Stuttgart: 2012
3i Comprehensive Enantioselective Organocatalysis. Dalko PI. Wiley-VCH; Weinheim: 2013

Special issues on asymmetric organocatalysis in:

3j Acc. Chem. Res. 2004; 37: 487-631
3k Top. Curr. Chem. 2009; 291: 1-460

Special issues on organocatalysis in:

3l Chem. Rev. 2007; 107: 5413-5883
3m Curr. Org. Chem. 2011; 15: 2082-2327

For applications of organocatalysis in the synthesis of natural products and non-natural biologically active molecules, see:

4a de Figueiredo RM, Christmann M. Eur. J. Org. Chem. 2007; 2575
4b Marqués-López E, Herrera RP, Christmann M. Nat. Prod. Rep. 2010; 27: 1138
4c Christmann M. Applications of Aminocatalysis in Target-Oriented Synthesis. In Asymmetric Organocatalysis: Science of Synthesis. Vol. 1. List B. Thieme; Stuttgart: 2012: 439
4d Marqués-López E, Herrera RP In Comprehensive Enantioselective Organocatalysis. Dalko PI. Wiley-VCH; Weinheim: 2013

For reviews on aminocatalysis, see:

5a Palomo C, Mielgo A. Angew. Chem. Int. Ed. 2006; 45: 7876
5b Mielgo A, Palomo C. Chem. Asian J. 2008; 3: 922
5c Barbas III CF. Angew. Chem. Int. Ed. 2008; 47: 42
5d Melchiorre P, Marigo M, Carlone A, Bartoli G. Angew. Chem. Int. Ed. 2008; 47: 6138
5e Bertelsen S, Jørgensen KA. Chem. Soc. Rev. 2009; 38: 2178
5f List B. Angew. Chem. Int. Ed. 2010; 49: 1730

For reviews about organocatalytic reactions catalyzed by chiral primary amines, see:

6a Peng F, Shao Z. J. Mol. Catal. A: Chem. 2008; 285: 1
6b Xu L.-W, Luo J, Lu Y. Chem. Commun. 2009; 1807

For reviews, see:

7a Mukherjee S, Yang JW, Hoffmann S, List B. Chem. Rev. 2007; 107: 5471
7b Phiko PM, Majander I, Erkkilä A. Top. Curr. Chem. 2010; 291: 29

For reviews, see:

8a Erkkilä A, Majander I, Phiko PM. Chem. Rev. 2007; 107: 5416
8b Brazier JB, Tomkinson NC. O. Top. Curr. Chem. 2010; 291: 281

For reviews on α-functionalization using enamine activation, see for example:

9a Marigo M, Jørgensen KA. Chem. Commun. 2006; 2001
9b Guillena G, Ramón DJ. Tetrahedron: Asymmetry 2006; 17: 1465

For reviews on conjugated additions using iminium ion activation see, for example:

10a Tsogoeva SB. Eur. J. Org. Chem. 2007; 1701
10b Almasi D, Alonso DA, Nájera C. Tetrahedron: Asymmetry 2007; 18: 299
10c Vicario JL, Badía D, Carrillo L. Synthesis 2007; 2065

For recent reviews on dienamine catalysis, see:

11a Ramachary DB, Reddy YV. Eur. J. Org. Chem. 2012; 865
11b Christmann M. Asymmetric Dienamine Activation. In Asymmetric Synthesis: More Methods and Applications. Christmann M, Bräse S. Wiley-VCH: Weinheim: 2012: 43

12 For a recent review on trienamine catalysis, see: Kumar I, Ramaraju P, Mir NA. Org. Biomol. Chem. 2013; 11: 709; and references cited therein

For pioneering work, see:

13a Chen S.-H, Hong B.-C, Su C.-F, Sarshar S. Tetrahedron Lett. 2005; 46: 8899
13b Bertelsen S, Marigo M, Brandes S, Dinér P, Jørgensen KA. J. Am. Chem. Soc. 2006; 128: 12973
13c Hong B.-C, Wu M.-F, Tseng H.-C, Liao J.-H. Org. Lett. 2006; 8: 2217
13d Bench BJ, Liu C, Evett CR, Watanabe CM. H. J. Org. Chem. 2006; 71: 9458
13e Utsumi N, Zhang H, Tanaka F, Barbas III CF. Angew. Chem. Int. Ed. 2007; 46: 1878

14a Marqués-López E, Herrera RP, Marks T, Jacobs WC, Könning D, de Figueiredo RM, Christmann M. Org. Lett. 2009; 11: 4116
14b Han B, Xiao Y.-C, He Z.-Q, Chen Y.-C. Org. Lett. 2009; 11: 4660
14c Han B, Xiao Y.-C, Yao Y, Chen Y.-C. Angew. Chem. Int. Ed. 2010; 49: 10189

15a Bencivenni G, Galzerano P, Mazzanti A, Bartoli G, Melchiorre P. Proc. Natl. Acad. Sci. U. S. A. 2010; 107: 20642
15b Bergonzini G, Vera S, Melchiorre P. Angew. Chem. Int. Ed. 2010; 49: 9685
15c Stiller J, Marqués-López E, Herrera RP, Fröhlich R, Strohmann C, Christmann M. Org. Lett. 2011; 13: 70
15d Silvi M, Cassania C, Morana A, Melchiorre P. Helv. Chim. Acta 2012; 95: 1985
15e Bastida D, Liu Y, Tian X, Escudero-Adán E, Melchiorre P. Org. Lett. 2013; 15: 220

16 For a recent example of organocascade reaction involving dienamine catalysis, see: Appayee C, Fraboni AJ, Brenner-Moyer SE. J. Org. Chem. 2012; 77: 8828

17a Hong B.-C, Tseng H.-C, Chen S.-H. Tetrahedron 2007; 63: 2840
17b Hong B.-C, Wu M.-F, Tseng H.-C, Huang G.-F, Su C.-F, Liao J.-H. J. Org. Chem. 2007; 72: 8459
17c de Figueiredo RM, Fröhlich R, Christmann M. Angew. Chem. Int. Ed. 2008; 47: 1450
17d Orue A, Reyes E, Vicario JL, Carrillo L, Uria U. Org. Lett. 2012; 14: 3740
17e Feng X, Zhou Z, Zhou R, Zhou Q.-Q, Dong L, Chen Y.-C. J. Am. Chem. Soc. 2012; 134: 19942

18a Han B, He Z.-Q, Li J.-L, Li R, Jiang K, Liu T.-Y, Chen Y.-C. Angew. Chem. Int. Ed. 2009; 48: 5474

For examples of inverse-electron-demand Diels–Alder reactions, see:

18b Li J.-L, Kang T.-R, Zhou S.-L, Li R, Wu L, Chen Y.-C. Angew. Chem. Int. Ed. 2010; 49: 6418
18c Li J.-L, Zhou S.-L, Chen P.-Q, Dong L, Liu T.-Y, Chen Y.-C. Chem. Sci. 2012; 3: 1879

For examples of asymmetric organocatalytic formal [2+2] cycloadditions, see:

19a Albrecht Ł, Dickmeiss G, Cruz Acosta F, Rodríguez-Escrich C, Davis RL, Jørgensen KA. J. Am. Chem. Soc. 2012; 134: 2543
19b Talavera G, Reyes E, Vicario JL, Carrillo L. Angew. Chem. Int. Ed. 2012; 51: 4104

20 Rauhut MM, Currier H. US 3074999, 1963
21 For a review on Rauhut–Currier reactions, see: Aroyan CE, Dermenci A, Miller SJ. Tetrahedron 2009; 65: 4069

For reviews on Morita–Baylis–Hillman reaction, see:

22a Masson G, Housseman C, Zhu J. Angew. Chem. Int. Ed. 2007; 46: 4614
22b Mansilla J, Saá JM. Molecules 2010; 15: 709
22c Basavaiah D, Reddy BS, Badsara SS. Chem. Rev. 2010; 110: 5447

23 Erguden JK, Moore HW. Org. Lett. 1999; 1: 375
24 Wang L.-C, Luis AL, Agapiou K, Jang H.-Y, Krische MJ. J. Am. Chem. Soc. 2002; 124: 2402

25a Frank SA, Mergott DJ, Roush WR. J. Am. Chem. Soc. 2002; 124: 2404
25b Thalji RK, Roush WR. J. Am. Chem. Soc. 2005; 127: 16778

26a Aroyan CE, Miller SJ. J. Am. Chem. Soc. 2007; 129: 256
26b Aroyan CE, Dermenci A, Miller SJ. J. Org. Chem. 2010; 75: 5784

For an example of the application of the Rauhut–Currier reaction in the synthesis of natural products, see:

26c Dermenci A, Selig PS, Domaoal RA, Spasov KA, Anderson KS, Miller SJ. Chem. Sci. 2011; 2: 1568

27 Gong J.-J, Li T.-Z, Pan K, Wu X.-Y. Chem. Commun. 2011; 47: 1491
28 Wang X.-F, Peng L, An J, Li C, Yang Q.-Q, Lu L.-Q, Gu F.-L, Xiao W.-J. Chem. Eur. J. 2011; 17: 6484

29a Takizawa S, Nguyen TM.-N, Grossmann A, Enders D, Sasai H. Angew. Chem. Int. Ed. 2012; 51: 5423
29b Takizawa S, Nguyen TM.-N, Grossmann A, Suzuki M, Enders D, Sasai H. Tetrahedron 2013; 69: 1202

30 Zhang X.-N, Shi M. Eur. J. Org. Chem. 2012; 6271
31 Jin Z, Yang R, Du Y, Tiwari B, Ganguly R, Chi YR. Org. Lett. 2012; 14: 3226
32 For a non-organocatalyzed example, see: Seidel F, Gladysz JA. Synlett 2007; 986

For other examples of intramolecular non-chiral Rauhut–Currier reaction, see:

33a Selig PS, Miller SJ. Tetrahedron Lett. 2011; 52: 2148
33b MacKay JA, Landis ZC, Motika SE, Kench MH. J. Org. Chem. 2012; 77: 7768

34a Zhong C, Chen Y, Petersen JL, Akhmedov NG, Shi X. Angew. Chem. Int. Ed. 2009; 48: 1279
34b Zhao Q.-Y, Pei C.-K, Guan X.-Y, Shi M. Adv. Synth. Catal. 2011; 353: 1973
34c Atienza RL, Scheidt KA. Aust. J. Chem. 2011; 64: 1158

For examples of aza-Rauhut–Currier reactions, see:

34d Shi Z, Yu P, Loh T.-P, Zhong G. Angew. Chem. Int. Ed. 2012; 51: 7825

For selected examples of non-enantioselective intermolecular Rauhut–Currier reactions, see:

35a Reynolds TE, Binkley MS, Scheidt KA. Org. Lett. 2008; 10: 2449
35b Yao W, Wu Y, Wang G, Zhang Y, Ma C. Angew. Chem. Int. Ed. 2009; 48: 9713
35c Shanbhag P, Nareddy PR, Dadwal M, Mobin MS, Namboothiri IN. N. Org. Biomol. Chem. 2010; 8: 4867

For examples of non-enantioselective Rauhut–Currier domino reactions, see:

35d Xie P, Huang Y, Lai W, Meng X, Chen R. Org. Biomol. Chem. 2011; 9: 6707
35e Ma J, Xie P, Hu C, Huang Y, Chen R. Chem. Eur. J. 2011; 17: 7418
35f Liu W, Zhou J, Zheng C, Chen X, Xiao H, Yang Y, Guo Y, Zhao G. Tetrahedron 2011; 67: 1768
35g Hu C, Geng Z, Ma J, Huang Y, Chen R. Chem. Asian J. 2012; 7: 2032

For examples of aza-Rauhut–Currier reactions, see:

35h Shi Z, Tong Q, Wen W, Leong Y, Zhong G. Chem. Eur. J. 2012; 18: 9802

For reviews on cyclopentenes, see:

36a Hudlicky T, Price JD. Chem. Rev. 1989; 89: 1467
36b Hartley RC, Caldwell ST. J. Chem. Soc., Perkin Trans. 1 2000; 477
36c Heasley B. Eur. J. Org. Chem. 2009; 1477

37 Tundis R, Loizzo MR, Menichini F, Statti GA, Menichini F. Mini-Rev. Med. Chem. 2008; 8: 399
38 Boros CA, Stermitz FR. J. Nat. Prod. 1990; 53: 1055

39a Tietze L.-F. Angew. Chem., Int. Ed. Engl. 1983; 22: 828
39b Villasenor IM. Anti-inflammatory Anti-allergy Agents Med. Chem. 2007; 6: 307

40 Kim HJ, Ruszczycky MW, Choi S.-h, Liu Y.-n, Liu H.-w. Nature (London) 2011; 473: 109

41a Lorenz M, Boland W, Dettner K. Angew. Chem., Int. Ed. Engl. 1993; 32: 912
41b Weibel DB, Oldham NJ, Feld B, Glombitza G, Dettner K, Boland W. Insect Biochem. Mol. Biol. 2001; 31: 583
41c Kunert M, Rahfeld P, Shaker KH, Schneider B, David A, Dettner K, Pasteels JM, Boland W. ChemBioChem 2013; 14: 353

For references of the effect of Brønsted acids in the Morita–Baylis–Hillman reaction, see:

42a Shi M, Liu Y. Org. Biomol. Chem. 2006; 4: 1468
42b Abermil N, Masson G, Zhu J. J. Am. Chem. Soc. 2008; 130: 12596
42c Yukawa T, Seelig B, Xu Y, Morimoto H, Matsunaga S, Berkessel A, Shibasaki M. J. Am. Chem. Soc. 2010; 132: 11988

43 Watanabe K, Takada Y, Matsuo N, Nishimura H. Biosci. Biotech. Biochem. 1996; 59: 1979
44 For the first total synthesis of (R)- and (S)-rotundial, see: Takikawa H, Yamazaki Y, Mori K. Eur. J. Org. Chem. 1998; 229
45 See the experimental section.

46a Seebach D, Grošelj U, Badine DM, Schweizer WB, Beck AK. Helv. Chim. Acta 2008; 91: 1999
46b Grošelj U, Schweizer WB, Ebert M.-O, Seebach D. Helv. Chim. Acta 2009; 92: 1

47 For theoretical discussions concerning dienamine intermediates, see: Duarte FJ. S, Cabrita EJ, Frenking G, Santos AG. Chem. Eur. J. 2009; 15: 1734
48 E/Z-Isomerization of the enol moiety of 5 could lead to an intramolecular attack of the iminium ion and to a dead end in the catalytic cycle.
49 Preparation of the ESI-HRMS sample: After 5 min of reaction, a 20-μL sample of the mixture was removed, and the solvent was evaporated. The residue was solved in MeCN (1 mL).
50 Schmid MB, Zeitler K, Gschwind RM. Angew. Chem. Int. Ed. 2010; 49: 4997

51a Weinges K, Ziegler HJ, Maurer W, Schmidbauer SB. Liebigs Ann. Chem. 1993; 1029
51b Yamane T, Takahashi M, Ogasawara K. Synthesis 1995; 444

52a Amri H, Villieras J. Tetrahedron Lett. 1987; 28: 5521
52b Bouyssi D, Monteire N, Balme G. Tetrahedron Lett. 1999; 40: 1297

53 Ohta H, Kobori T, Fujisawa T. J. Org. Chem. 1977; 42: 1231
54 Wilson RM, Jen WS, MacMillan DW. C. J. Am. Chem. Soc. 2005; 127: 11616
55 X ray crystallographic analysis data for 27. CCDC 813588 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
56 The absolute configuration for compounds 21a,b and 27 was not assigned unambiguously.
57 For more details see Supporting Information.
58 The synthesis of the products as racemic mixtures were carried out using a mixture of both enantiomers of the catalyst [(S)-IV/(R)-IV) 1:1].

59a Amri H, Rambaud M, Villieras J. Tetrahedron 1990; 46: 3535
59b Nagata H, Ogasawara K. Tetrahedron Lett. 1999; 40: 6617

Zusatzmaterial

Supporting Information