Chiral Brønsted Acids
and Their Calcium Salts in Catalytic Asymmetric Mannich
Reactions of Cyclic 1,3-Diketones

Magnus Rueping; Teerawut Bootwicha; Erli Sugiono

doi:10.1055/s-0030-1259318

LETTER

Chiral Brønsted Acids and Their Calcium Salts in Catalytic Asymmetric Mannich Reactions of Cyclic 1,3-Diketones

Magnus Rueping*, Teerawut Bootwicha, Erli Sugiono
Institute of Organic Chemistry, RWTH-Aachen University, Landoltweg 1, 52074 Aachen, Germany
Fax: +49(241)8092665; e-Mail: Magnus.Rueping@rwth-aachen.de;

Abstract

Alle Artikel dieser Rubrik

Abstract

Asymmetric calcium-catalyzed direct Mannich reactions of 1,3-dicarbonyl compounds with imines have been developed. The reactions proceed under mild conditions and provide the corresponding products with high enantiomeric excess.

Key words

Mannich reaction - organocatalysis - calcium - BINOL phosphoric acid - amino acid

Volltext

Referenzen

References and Notes

For reviews on asymmetric Mannich reactions, see:

1a Arend M. Westermann B. Risch N. Angew. Chem. Int. Ed. 1998, 37: 1044

1b Kobayashi S. Ishitani H. Chem. Rev. 1999, 99: 1069

1c Jarvo ER. Miller SJ. Tetrahedron 2002, 58: 2481

1d Cordova A. Acc. Chem. Res. 2004, 37: 102

1e List B. Acc. Chem. Res. 2004, 37: 548

1f Friestad GK. Mathies AK. Tetrahedron 2007, 63: 2541

1g Ting A. Schaus SE. Eur. J. Org. Chem. 2007, 5797

1h Verkade JMM. van Hemert LJC. Quaedflieg PJLM. Rutjes FPJT. Chem. Soc. Rev. 2008, 37: 29

For reviews on chiral BINOL-derived phosphoric acid diesters, see:

2a Akiyama T. Itoh J. Fuchibe K. Adv. Synth. Catal. 2006, 348: 999

2b Akiyama T. Chem. Rev. 2007, 107: 5744

2c Kampen D. Reisinger CM. List B. Top. Curr. Chem. 2009, 291: 395

2d Terada M. Chem. Commun. 2008, 4097

2e Terada M. Bull. Chem. Soc. Jpn. 2010, 83: 101

2f Terada M. Synthesis 2010, 1929

For selected examples, see:

3a Storer RI. Carrera DE. Ni Y. MacMillan DWC. J. Am. Chem. Soc. 2006, 128: 84

3b Wanner MJ. van der Haas RNS. de Cuba KR. van Maarseveen JH. Hiemstra H. Angew. Chem. Int. Ed. 2007, 46: 7485

3c Rowland EB. Rowland GB. Rivera-Otero E. Antilla JC. J. Am. Chem. Soc. 2007, 129: 12084

3d Baudequin C. Zamfir A. Tsogoeva SB. Chem. Commun. 2008, 4637

3e Ackermann L. Althammer A. Synlett 2008, 995

3f Cheng X. Goddard R. Buth G. List B. Angew. Chem. Int. Ed. 2008, 47: 5079

3g Liu H. Dagousset G. Masson G. Retailleau P. Zhu J. J. Am. Chem. Soc. 2009, 131: 4598

3h Sun F.-L. Zeng M. Gu Q. You S.-L. Chem. Eur. J. 2009, 15: 8709

3i Terada M. Machioka K. Sorimachi K. Angew. Chem. Int. Ed. 2009, 48: 2553

3j Akiyama T. Katoh T. Mori K. Angew. Chem. Int. Ed. 2009, 48: 4226

3k Yue T. Wang M.-X. Wang D.-X. Masson G. Zhu J. Angew. Chem. Int. Ed. 2009, 48: 6717

3l Lu M. Zhu D. Lu Y. Zeng X. Tan B. Xu Z. Zhong G. J. Am. Chem. Soc. 2009, 131: 4562

3m Terada M. Toda Y. J. Am. Chem. Soc. 2009, 131: 6354

3n Zhang Q.-W. Fan C.-A. Zhang H.-J. Tu Y.-Q. Zhao Y.-M. Gu P. Chen Z.-M. Angew. Chem. Int. Ed. 2009, 48: 8572

3o Zeng X. Zeng X. Xu Z. Lu M. Zhong G. Org. Lett. 2009, 11: 3036

3p Müller S. List B. Angew. Chem. Int. Ed. 2009, 48: 9975

3q Ube H. Shimada N. Terada M. Angew. Chem. Int. Ed. 2010, 49: 1858

3r Lv J. Li X. Zhong L. Luo S. Cheng J.-P. Org. Lett. 2010, 12: 1096

3s Cox DJ. Smith MD. Fairbanks AJ. Org. Lett. 2010, 12: 1452

3t Bergonzini G. Gramigna L. Mazzanti A. Fochi M. Bernardi L. Ricci A. Chem. Commun. 2010, 46: 327

For selected examples from our group, see:

4a Rueping M. Sugiono E. Azap C. Theissmann T. Bolte M. Org. Lett. 2005, 7: 3781

4b Rueping M. Sugiono E. Azap C. Angew. Chem. Int. Ed. 2006, 45: 2617

4c Rueping M. Ieawsuwan W. Antonchick AP. Nachtsheim BJ. Angew. Chem. Int. Ed. 2007, 46: 2097

4d Rueping M. Sugiono E. Moreth SA. Adv. Synth. Catal. 2007, 349: 759

4e Rueping M. Sugiono E. Theissmann T. Kuenkel A. Köckritz A. Pews-Davtyan A. Nemati N. Beller M. Org. Lett. 2007, 9: 1065

4f Rueping M. Nachtsheim BJ. Moreth SA. Bolte M. Angew. Chem. Int. Ed. 2008, 47: 593

4g Rueping M. Antonchick AP. Org. Lett. 2008, 10: 1731

4h Rueping M. Theissmann T. Kuenkel A. Koenigs RM. Angew. Chem. Int. Ed. 2008, 47: 6798

4i Rueping M. Antonchick AP. Sugiono E. Grenader K. Angew. Chem. Int. Ed. 2009, 48: 908

4j Rueping M. Sugiono E. Steck A. Theissmann T. Adv. Synth. Catal. 2010, 352: 281

4k Rueping M. Tato F. Schoepke FR. Chem. Eur. J. 2010, 16: 2688

5a Akiyama T. Itoh J. Yokota K. Fuchibe K. Angew. Chem. Int. Ed. 2004, 43: 1566

5b Yamanaka M. Itoh J. Fuchibe K. Akiyama T. J. Am. Chem. Soc. 2007, 129: 6756

5c Itoh J. Fuchibe K. Akiyama T. Synthesis 2008, 1319

5d Akiyama T. Katoh T. Mori K. Kanno K. Synlett 2009, 1664

6a Uraguchi D. Terada M. J. Am. Chem. Soc. 2004, 126: 5356

6b Gridnev ID. Kouchi M. Sorimachi K. Terada M. Tetrahedron Lett. 2007, 48: 497

6c Terada M. Machioka K. Sorimachi K. Angew. Chem. Int. Ed. 2006, 45: 2254

6d Terada M. Machioka K. Sorimachi K.
J. Am. Chem. Soc. 2007, 129: 10336

6e Terada M. Tanaka H. Sorimachi K. Synlett 2008, 1661

6f Hatano M. Moriyama K. Maki T. Ishihara K. Angew. Chem. Int. Ed. 2010, 49: 3823

7a Guo Q.-X. Liu H. Guo C. Luo S.-W. Gu Y. Gong L.-Z. J. Am. Chem. Soc. 2007, 129: 3790

7b Dagousset G. Drouet F. Masson G. Zhu J. Org. Lett. 2009, 11: 5546

8a Akiyama T. Honma Y. Itoh J. Fuchibe K. Adv. Synth. Catal. 2008, 350: 399

8b Sickert M. Schneider C. Angew. Chem. Int. Ed. 2008, 47: 3631

8c Giera DS. Sickert M. Schneider C. Synthesis 2009, 3797

8d Sickert M. Abels F. Lang M. Sieler J. Birkemeyer C. Schneider C. Chem. Eur. J. 2010, 16: 2806

For selected recent examples of organocatalytic asymmetric direct Mannich reactions, see:

9a Lou S. Taoka BM. Ting A. Schaus SE. J. Am. Chem. Soc. 2005, 127: 11256

9b Enders D. Grondal C. Vrettou M. Raabe G. Angew. Chem. Int. Ed. 2005, 44: 4079

9c Ting A. Lou S. Schaus SE. Org. Lett. 2006, 8: 2003

9d Enders D. Grondal C. Vrettou M. Synthesis 2006, 3597

9e Zhao G.-L. Córdova A. Tetrahedron Lett. 2006, 47: 7417

9f Hasegawa A. Naganawa Y. Fushimi M. Ishihara K. Yamamoto H. Org. Lett. 2006, 8: 3175

9g Tillman AL. Dixon DJ. Org. Biomol. Chem. 2007, 5: 606

9h Cheng L. Wu X. Lu Y. Org. Biomol. Chem. 2007, 5: 1018

9i Marianacci O. Micheletti G. Bernardi L. Fini F. Fochi M. Pettersen D. Sgarzani V. Ricci A. Chem. Eur. J. 2007, 13: 8338

9j Ramasastry SSV. Zhang H. Tanaka F. Barbas CF. J. Am. Chem. Soc. 2007, 129: 288

9k Sukach VA. Golovach NM. Pirozhenko VV. Rusanov EB. Vovk MV. Tetrahedron: Asymmetry 2008, 19: 761

9l Kawanaka Y. Phillips EM. Scheidt KA.
J. Am. Chem. Soc. 2009, 131: 18028

9m Pan Y. Zhao Y. Ma T. Yang Y. Liu H. Jiang Z. Tan C.-H. Chem. Eur. J. 2010, 16: 779

9n Ayaz M. Westermann B. Synlett 2010, 1489

10a Rueping M. Azap C. Angew. Chem. Int. Ed. 2006, 45: 7832

10b Rueping M. Sugiono E. Schoepke FR. Synlett 2007, 1441

10c Rueping M. Lin MY. Chem. Eur. J. 2010, 16: 4169

For selected examples of chiral Ca(II) salts in catalysis, see:

11a Suzuki T. Yamagiwa N. Matsuo Y. Sakamoto S. Yamaguchi K. Shibasaki M. Noyori R. Tetrahedron Lett. 2001, 42: 4669

11b Kumaraswamy G. Sastry MNV. Jena N. Tetrahedron Lett. 2001, 42: 8515

11c Saito S. Tsubogo T. Kobayashi S. J. Am. Chem. Soc. 2007, 129: 5364

11d Tsubogo T. Saito S. Seki K. Yamashita Y. Kobayashi S. J. Am. Chem. Soc. 2008, 130: 13321

11e Kobayashi S. Tsubogo T. Saito S. Yamashita Y. Org. Lett. 2008, 10: 807

11f Poisson T. Yamashita Y. Kobayashi S. J. Am. Chem. Soc. 2010, 132: 7890

11g Poisson T. Tsubogo T. Yamashita Y. Kobayashi S. J. Org. Chem. 2010, 75: 963

For our studies on chiral calcium salts in catalysis, see:

12a Rueping M. Theissmann T. Kuenkel A. Koenigs RM. Angew. Chem. Int. Ed. 2008, 47: 6798

12b Rueping M. Koenigs RM. Atodiresei I. Chem. Eur. J. 2010, 16: 9350

12c Rueping M. Nachtsheim BJ. Koenigs RM. Ieawsuwan W. Chem. Eur. J. 2010, 16: 13116

13a Adair G. Mukherjee S. List B. Aldrichimica Acta 2008, 41: 31

13b Klussmann M. Ratjen L. Hoffmann S. Wakchaure V. Goddard R. List B. Synlett 2010, 2189

14

The absolute configuration of the products was obtained from X-ray crystal structure analysis of compound 6c. On the basis of this structure the absolute configuration was assigned to be the S configuration.

15

General Procedure for Direct Mannich Reaction: In a typical experiment pyrone 2 or 1,3-cyclohexadione (5; 1.0 equiv), aldimine 3 (1.5 equiv), and the calcium catalyst (5 mol%) were suspended in Bu₂O in a screw-capped vial and the resulting mixture was allowed to stir at -40 ˚C for 60-72 h. Purification of the crude product by column chromatography on silica gel afforded the corresponding product 4 or 6.
( R )- tert -Butyl(4-hydroxy-6-methyl-2-oxo-2 H -pyran-3-yl)( p -tolyl)methylcarbamate (4a): Isolated by column chromatography (CH₂Cl₂-acetone, 10:1) as a white solid in 49% yield and 88% ee. The ee was determined by HPLC using Chiralpak AD-H column [(n-hexane-i-PrOH, 90:10), flow rate: 0.6 mL/min; major enantiomer: t _R = 29.59 min; minor enantiomer: t _R = 22.07 min]; [α]_D -6.1 (c = 1.84, CH₂Cl₂); mp 173-175 ˚C. ^¹H NMR (400 MHz, CDCl₃): δ = 7.22 (d, J = 8.0 Hz, 2 H), 7.02 (d, J = 8.0 Hz, 2 H), 6.79 (d, J = 12.0 Hz, 1 H), 6.05 (d, J = 12.0 Hz, 1 H), 5.88 (s, 1 H), 3.41 (s, 1 H), 2.23 (s, 3 H), 2.07 (s, 3 H), 1.39 (s, 9 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 166.10, 164.94, 161.74, 157.40, 137.67, 136.82, 129.09, 126.12, 102.60, 100.84, 81.11, 28.48, 21.05, 19.85. IR (KBr): 3359, 2980, 1700, 1651, 1530, 1161, 884, 783 cm^-¹. MS (EI): m/z (%) = 345 (2) [M⁺], 339 (30), 251 (41), 230 (58), 200(100), 145 (64), 77 (92).
( R )- tert -Butyl(2-hydroxy-6-oxocyclohex-1-enyl)( p -tolyl)-methylcarbamate (6a): Isolated by column chromatography (CH₂Cl₂-acetone, 10:1) as a white solid in 47% yield and 73% ee. The ee was determined by HPLC using Chiralpak AD-H column [(n-hexane-i-PrOH, 92:8), flow rate: 0.6 mL/min; major enantiomer: t _R = 20.23 min; minor enantiomer: t _R = 17.98 min]; [α]_D +4.43 (c = 0.75, CH₂Cl₂); mp 132-134 ˚C. ^¹H NMR (400 MHz, CDCl₃): δ = 10.60 (br s, 1 H), 7.19 (d, J = 8.0 Hz, 2 H), 7.00 (d, J = 8.0 Hz, 2 H), 6.82 (d, J = 9.9 Hz, 1 H), 5.99 (d, J = 9.9 Hz, 1 H), 2.45 (t, J = 6.0 Hz, 2 H), 2.22 (s, 5 H), 1.79-1.89 (m, 2 H), 1.35 (s, 9 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 173.73, 157.32, 136.00, 128.80, 125.92, 116.22, 80.60, 48.78, 37.02, 29.64, 28.54, 21.15, 20.62. IR (KBr): 3455, 2922, 1710, 1490, 1165, 1025, 779 cm^-¹. MS (EI): m/z (%) = 331 (56) [M⁺], 266 (58), 239 (92), 194 (100), 116 (58), 78 (52), 70 (98).