Planar and Central Chiral [2.2]Paracyclophanes as Powerful Catalysts for Asymmetric 1,2-Addition Reactions

Stefan Bräse; Stefan Dahmen; Sebastian Höfener; Frank Lauterwasser; Michael Kreis; Robert E. Ziegert

doi:10.1055/s-2004-836029

ACCOUNT

Planar and Central Chiral [2.2]Paracyclophanes as Powerful Catalysts for Asymmetric 1,2-Addition Reactions

Stefan Bräse*^a, Stefan Dahmen*^b, Sebastian Höfener^a, Frank Lauterwasser^a, Michael Kreis^a, Robert E. Ziegert^c
^a Institut für Organische Chemie, Universität Karlsruhe (TH), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany
^b cynora GmbH, Kaiserstr. 100, 52134 Herzogenrath, Germany, www.cynora.de
^c Kekulé-Institut für Organische Chemie und Biochemie, Rheinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Straße 1, 53121 Bonn, Germany
Fax: +49(721)6088581; e-Mail: braese@ioc.uka.de;

Abstract

All articles of this category

Abstract

Planar and central chiral [2.2]paracyclophane ligands have been designed and used in the highly enantioselective addition of alkyl, alkenyl, alkynyl and aryl zinc reagents to aldehydes and imines.

1 Why Use [2.2]Paracyclophanes as Chiral Ligands?

2 Synthesis of [2.2]Paracyclophane Ligands

2.1 Preparation and Resolution of FHPC, AHPC and BHPC-Based Imines

2.2 Synthesis of Further Imines Based on FHPC and AHPC

2.3 Synthesis of Chiral Amine Ligands

2.4 1,2-Addition to Imines

2.5 Reductive Amination

2.6 Structural Information on AHPC-Based Imines

2.7 Synthesis of Enantiomerically Pure Thio-Substituted Paracyclophanes

2.8 Other Cyclophane-Based Ligands Used for Asymmetric 1,2-Addition Reactions

3 Asymmetric 1,2-Addition Reactions to Aryl Aldehydes

3.1 Initial Considerations

3.2 Mechanistic Investigations

3.3 Reactivity of [2.2]Paracyclophane Ligands

3.4 Asymmetric Addition Reactions to Aromatic Aldehydes: Scope of Substrates

4 Asymmetric Addition Reactions to Aliphatic Aldehydes

5 Addition of Alkenyl Zinc Reagents to Aldehydes

6 Addition of Alkynyl Zinc Reagents to Aldehydes

7 Addition of Phenylzinc to Aldehydes

8 Asymmetric Addition Reactions to Imines

9 Asymmetric Addition Reactions on Solid Supports

10 Conclusions and Outlook

11 Abbreviations

Key words

asymmetric catalysis - ligands - paracyclophanes - zinc - nucleophilic additions

Full Text

References

<A NAME="RA35304ST-1">1</A> Knowles WS. Sabacky M. J. Chem. Soc., Chem. Commun. 1968, 1445

<A NAME="RA35304ST-2">2</A> Kagan HB. Dang TP. J. Am. Chem. Soc. 1972, 94: 6429

<A NAME="RA35304ST-3">3</A> Noyori R. Science 1990, 248: 1194

<A NAME="RA35304ST-4A">4a</A> Knowles WS. Angew. Chem. Int. Ed. 2002, 41: 1996 ; Angew. Chem. 2002, 114, 2096

<A NAME="RA35304ST-4B">4b</A> Noyori R. Angew. Chem. Int. Ed. 2002, 41: 2008 ; Angew. Chem. 2002, 114, 2108

<A NAME="RA35304ST-4C">4c</A> Sharpless KB. Angew. Chem. Int. Ed. 2002, 41: 2024 ; Angew. Chem. 2002, 114, 2126

<A NAME="RA35304ST-5">5</A> Stinson SC. Chem. Eng. News 2001, 79: 45

<A NAME="RA35304ST-6A">6a</A> Reich HJ. Cram DJ. J. Am. Chem. Soc. 1969, 91: 3527

<A NAME="RA35304ST-6B">6b</A> Cram DJ. Steinberg H. J. Am. Chem. Soc. 1951, 73: 5691

<A NAME="RA35304ST-7A">7a</A> Pye PJ. Rossen K. Reamer RA. Tsou NN. Volante RP. Reider PJ. J. Am. Chem. Soc. 1997, 119: 6207

<A NAME="RA35304ST-7B">7b</A> Rossen K. Reamer RA. Volante RP. Reider PJ. Tetrahedron Lett. 1998, 39: 4441

<A NAME="RA35304ST-7C">7c</A> Rossen K. Pye PJ. Maliakal A. Volante RP. J. Org. Chem. 1997, 62: 6462

<A NAME="RA35304ST-8">8</A> Gibson S. Knight JD. Org. Biomol. Chem. 2003, 1: 1256

<A NAME="RA35304ST-9">9</A> Bräse S. Lauterwasser F. Ziegert RE. Adv. Synth. Catal. 2003, 345: 869

<A NAME="RA35304ST-10">10</A> Helmchen G. Pfaltz A. Acc. Chem. Res. 2000, 33: 336

<A NAME="RA35304ST-11">11</A> Vetter AH. Berkessel A. Tetrahedron Lett. 1998, 39: 1741

<A NAME="RA35304ST-12A">12a</A> Rozenberg V. Kharitonov V. Antonov D. Sergeeva E. Aleshkin A. Ikonnikov N. Orlova S. Belokon Y. Angew. Chem., Int. Ed. Engl. 1994, 33: 91 ; Angew. Chem. 1994, 106, 106

<A NAME="RA35304ST-12B">12b</A> Antonov D. Belokon YN. Ikonnikov NS. Orlova SA. Pisaevsky AP. Raevski NI. Rozenberg VI. Sergeeva EV. Struchkov YT. Tararov VI. Vorontsov EV. J. Chem. Soc., Perkin Trans. 1 1995, 1873

<A NAME="RA35304ST-13">13</A> Rozenberg V. Danilova T. Sergeeva E. Vorontsov E. Starikova Z. Lysenko K. Belokon Y. Eur. J. Org. Chem. 2000, 3295

<A NAME="RA35304ST-14A">14a</A> Pastor SD. Togni A. J. Am. Chem. Soc. 1989, 111: 2333

<A NAME="RA35304ST-14B">14b</A> Togni A. Pastor SD. J. Org. Chem. 1990, 55: 1649

<A NAME="RA35304ST-14C">14c</A> Pastor SD. Togni A. Helv. Chim. Acta 1991, 74: 905

The term ‘Chiral Cooperativity’ was used by Pastor and Togni to describe positive interaction of different chiral moieties surpassing their mere addition. The case of diminishing was not investigated by the authors. Therefore they used ‘not cooperative’ in the case of a ‘mismatched pair’.

<A NAME="RA35304ST-15A">15a</A> Masamune S. Choy W. Petersen JS. Sita LR. Angew. Chem., Int. Ed. Engl. 1985, 24: 1 ; Angew. Chem. 1985, 97, 1

<A NAME="RA35304ST-15B">15b</A> Heathcock CH. White CT. J. Am. Chem. Soc. 1979, 101: 7076

<A NAME="RA35304ST-15C">15c</A> Horeau A. Kagan H.-B. Vigneron J.-P. Bull. Soc. Chim. Fr. 1968, 3795

<A NAME="RA35304ST-16A">16a</A> Hayashi T. Tajika M. Tamao K. Kumada M. J. Am. Chem. Soc. 1976, 98: 3718

<A NAME="RA35304ST-16B">16b</A> Hayashi T. Konishi M. Fukushima M. Mise T. Kagotani M. Tajika M. Kumada M. J. Am. Chem. Soc. 1982, 104: 180

<A NAME="RA35304ST-17A">17a</A> Bolm C. Muniz-Fernández K. Seger A. Raabe G. Günther K. J. Org. Chem. 1998, 63: 7860

<A NAME="RA35304ST-17B">17b</A> Bolm C. Muniz K. Hildebrand JP. Org. Lett. 1999, 1: 491

For studies on chiral cooperativity in axial- and central-chiral ligands, see:

<A NAME="RA35304ST-18A">18a</A> Buisman GJH. van der Veen LA. Klootwijk A. de Lange WGI. Kamer PCJ. van Leeuwen PWNM. Vogt D. Organometallics 1997, 16: 2929

<A NAME="RA35304ST-18B">18b</A> Cserépi-Szûcs S. Tóth I. Párkányi L. Bakos J. Tetrahedron: Asymmetry 1998, 9: 3135

<A NAME="RA35304ST-18C">18c</A> Cserépi-Szûcs S. Huttner G. Zsolnai L. Szölõsy A. Hegedüs C. Bakos J. Inorg. Chim. Acta 1999, 296: 222

<A NAME="RA35304ST-19A">19a</A> Hopf H. Barrett DG. Liebigs Ann. 1995, 449

<A NAME="RA35304ST-19B">19b</A> Cipiciani A. Fringuelli F. Mancini V. Piermatti O. Pizzo F. Ruzziconi R. J. Org. Chem. 1997, 62: 3744

<A NAME="RA35304ST-19C">19c</A> Pamperin D. Schulz C. Hopf H. Syldatk C. Pietzsch M. Eur. J. Org. Chem. 1998, 1441

<A NAME="RA35304ST-19D">19d</A> Rozenberg V. Danilova T. Sergeeva E. Vorontsov E. Starikova Z. Korlyukov A. Hopf H. Eur. J. Org. Chem. 2002, 468

<A NAME="RA35304ST-20A">20a</A> Hoffmann RW. Ditrich K. Synthesis 1983, 107

<A NAME="RA35304ST-20B">20b</A> Krohn K. Rieger H. Hopf H. Barrett D. Jones PG. Doring D. Chem. Ber. 1990, 123: 1729

<A NAME="RA35304ST-21">21</A> Dahmen S. Bräse S. Tetrahedron: Asymmetry 2001, 12: 2845

<A NAME="RA35304ST-22">22</A> Sergeeva EV. Rozenberg VI. Vorontsov EV. Danilova TI. Starikova ZA. Yanovsky AI. Belokon YN. Hopf H. Tetrahedron: Asymmetry 1996, 7: 3445

<A NAME="RA35304ST-23">23</A> Kane VV. Gerdes A. Grahn W. Ernst L. Dix I. Jones PG. Hopf H. Tetrahedron Lett. 2001, 42: 373

<A NAME="RA35304ST-24A">24a</A> Cipiciani A. Fringuelli F. Mancini V. Piermatti O. Scappini AM. Ruzziconi R. Tetrahedron 1997, 53: 11853

<A NAME="RA35304ST-24B">24b</A> Pamperin D. Schulz C. Hopf H. Syldatk C. Pietzsch M. Eur. J. Org. Chem. 1998, 1441

Kreis, M. unpublished results.

<A NAME="RA35304ST-26">26</A> Still IWJ. Natividad-Preyra R. Toste FD. Can. J. Chem. 1999, 77: 113

<A NAME="RA35304ST-27">27</A> Miranda EI. Díaz MJ. Rosado I. Soderquist JA. Tetrahedron Lett. 1994, 50: 3221

<A NAME="RA35304ST-28">28</A> Wipf P. Kendall C. Chem.-Eur. J. 2002, 8: 1778

<A NAME="RA35304ST-29">29</A> Danilova T. Rozenberg V. Vorontsov EV. Starikova Z. Hopf H. Tetrahedron: Asymmetry 2003, 14: 1375

<A NAME="RA35304ST-30">30</A> Danilova T. Rozenberg VI. Sergeeva EV. Starikova ZA. Bräse S. Tetrahedron: Asymmetry 2003, 14: 2013

The transfer of the planar cylopentadienyl moiety of the ferrocene to benzenederivatives as done by Bolm et al. is risky, because of the change of the ortho-angle from 72° for the ferrocene to 60° for the benzenederivatives. These changes in the molecule geometry make it extremely difficult to derive the exact nature of the transition state from the one of the ferrocene.

To give the reader the opportunity to compare the results of the catalysis directly with the ligand structure, we do this without a detailed summary of the reactions. Further in this chapter, we will only show the catalyst and its results in the diethylzinc addition to benzaldehyde with the conditions as shown in Scheme [12] .

<A NAME="RA35304ST-33">33</A> Dahmen S. PhD Thesis RWTH Aachen: 2002.

Lauterwasser, F. unpublished results.

Energy minimization of the corresponding conformers were done with Chem3D Pro and CS MOPAC Pro.

In a PM3 calculation of the conformers done by J. Rudolph with the program Spartan 2001 (Wavefunction Inc., California) the results of the MNDO-analysis werde confirmed, resulting in conformer A as the conformer with the lowest energy. Although the differences in energy by this method are only 5 kcal/mol and therefore a bit lower as with MNDO, they are still high enough to make any consideration of the conformer B superfluous. (1 kcal = 4.1868 kJ).

The energy differences of the µ-O structures are only between 1-3 kcal/mol.

<A NAME="RA35304ST-38A">38a</A> Goldfuss B. Houk KN. J. Org. Chem. 1998, 63: 8998

<A NAME="RA35304ST-38B">38b</A> Goldfuss B. Steigelmann M. Khan SI. Houk KN. J. Org. Chem. 2000, 65: 77

<A NAME="RA35304ST-39">39</A> Rasmussen T. Norrby P.-O. J. Am. Chem. Soc. 2001, 123: 2464

<A NAME="RA35304ST-40A">40a</A> Kitamura M. Suga S. Oka H. Noyori R. J. Am. Chem. Soc. 1998, 120: 9800

Dahmen, S.; Lauterwasser, F.; Vanderheiden, S.; Bräse, S. unpublished.

<A NAME="RA35304ST-40C">40c</A> Wipf P. Pierce JG. Wang X. Tetrahedron: Asymmetry 2003, 14: 3605 ; and references cited therein

<A NAME="RA35304ST-41">41</A> Dahmen S. Bräse S. Chem. Commun. 2002, 26

<A NAME="RA35304ST-42">42</A> Nugent WA. Org. Lett. 2002, 4: 2133

<A NAME="RA35304ST-43">43</A> Höfener S. Lauterwasser F. Bräse S. Adv. Synth. Catal. 2004, 346: 755

<A NAME="RA35304ST-44">44</A> Dahmen S. Bräse S. unpublished

Allyl alcohols are substrates for, e.g., cyclopropanation reactions, aziridination reactions, ene-reactions, epoxidations, dihydroxylations, methoxy selenations, iodo hydroxylations, brominations, and allylic substitution reactions.

<A NAME="RA35304ST-46A">46a</A> Oppolzer W. Radinov RN. Tetrahedron Lett. 1988, 29: 5645

<A NAME="RA35304ST-46B">46b</A> Oppolzer W. Radinov RN. Tetrahedron Lett. 1991, 32: 5777

<A NAME="RA35304ST-47A">47a</A> Noyori R. Kitamura M. Angew. Chem., Int. Ed. Engl. 1991, 30: 49

<A NAME="RA35304ST-47B">47b</A> Kitamura M. Suga S. Kawai K. Noyori R. J. Am. Chem. Soc. 1986, 108: 6071

<A NAME="RA35304ST-48A">48a</A> Oppolzer W. Radinov RN. Helv. Chim. Acta 1992, 75: 170

<A NAME="RA35304ST-48B">48b</A> This reaction was recently extended to intramolecular cyclization reactions: Oppolzer W. Radinov RN. El-Sayed E. J. Org. Chem. 2001, 66: 4766

The addition of vinylzinc has also been studied:

<A NAME="RA35304ST-49A">49a</A> von dem Bussche-Hünnefeld JL. Seebach D. Tetrahedron 1992, 48: 5719

<A NAME="RA35304ST-49B">49b</A> Soai K. Takahashi K. J. Chem. Soc., Perkin Trans. 1 1994, 1257

<A NAME="RA35304ST-49C">49c</A> Shibata T. Nakatsui K. Soai K. Inorg. Chim. Acta 1999, 296: 33

<A NAME="RA35304ST-50A">50a</A> Wipf P. Xu W. Tetrahedron Lett. 1994, 35: 5197

<A NAME="RA35304ST-50B">50b</A> Wipf P. Xu W. Org. Synth. 1997, 74: 205

<A NAME="RA35304ST-50C">50c</A> Wipf P. Ribe S. J. Org. Chem. 1998, 63: 6454

<A NAME="RA35304ST-51">51</A> Dahmen S. Bräse S. Org. Lett. 2001, 3: 4119

Using these modifications, the aldehyde could be added in one portion, which is a significant practical improvement over the original Oppolzer protocol, where the aldehyde had to be added over a period of 20 min to obtain high enantioselectivities.

The absolute configuration was assigned by comparison of the optical rotation with the literature known compounds (S)-1-(4-chlorophenyl)hept-2-en-1-ol and (S)-1-phenylnon-2-en-1-ol, respectively, and the assumption of a unanimous reaction pathway for all other aldehyde substrates. The absolute configuration of the allyl alcohol products 51 is consistent with the induction observed in the diethylzinc addition to aldehydes with the ligands 5a and 6a.

<A NAME="RA35304ST-54A">54a</A> Nehl H. Scheidt W. J. Organomet. Chem. 1985, 289: 1

<A NAME="RA35304ST-54B">54b</A> Mynott R. Gabor B. Lehmkuhl H. Doering I. Angew. Chem., Int. Ed. Engl. 1985, 24: 335

<A NAME="RA35304ST-55A">55a</A> Bolm C. Hermanns N. Hildebrand JP. Muniz K. Angew. Chem. Int. Ed. 2000, 39: 3465 ; Angew. Chem. 2000, 112, 3607

<A NAME="RA35304ST-55B">55b</A> Blacker J. In Proceedings of the 3rd International Conference on the Scale Up of Chemical Processes Laird T. Scientific Update; Mayfieldn / East Sussex / Great Britain: 1998.

<A NAME="RA35304ST-56">56</A> Alvaro G. Pacioni P. Savoia D. Chem.-Eur. J. 1997, 3: 726

<A NAME="RA35304ST-57">57</A> Modern Acetylene Chemistry Stang PJ. Diederich F. VCH; Weinheim: 1995.

<A NAME="RA35304ST-58">58</A> For a recent review, see: Pu L. Tetrahedron 2003, 59: 9873

<A NAME="RA35304ST-59">59</A> Ishizaki M. Hoshino O. Tetrahedron: Asymmetry 1994, 5: 1901

<A NAME="RA35304ST-60A">60a</A> Frantz DE. Fässler R. Carreira EM. J. Am. Chem. Soc. 2000, 122: 1806

<A NAME="RA35304ST-60B">60b</A> Boyall D. López F. Sasaki H. Frantz D. Carreira EM. Org. Lett. 2000, 2: 4233

<A NAME="RA35304ST-60C">60c</A> Frantz DE. Fässler R. Tomooka CS. Carreira EN. Acc. Chem. Res. 2000, 33: 373

<A NAME="RA35304ST-60D">60d</A> Anand NK. Carreira EN. J. Am. Chem. Soc. 2001, 123: 9687

Zn(OTf)₂ is ten times more expensive than diethylzinc: Zn(OTf)₂: 10 g 46.80 $ ( = 1 $/mmol), Et₂Zn in hexane: 100 g (810 mmol) 80.90 $ (= 0.1 $/mmol). Prices taken from Acros Organics.

<A NAME="RA35304ST-62">62</A> Xu M.-H. Pu L. Org. Lett. 2002, 4: 4555

<A NAME="RA35304ST-63">63</A> Bolm C. Rudolph J. J. Am. Chem. Soc. 2002, 124: 14850

This behavior is untypical for mixed zinc species. The equilibrium could be influenced by the very low solubility of the dialkynylzinc reagents.

The clear supernant solution gives rise to the ethylation product in >80% yield.

For selected references in this field, see:

<A NAME="RA35304ST-66A">66a</A> Bolm C. Hildebrand JP. Muniz K. Hermanns N. Angew. Chem. Int. Ed. 2001, 40: 3284 ; Angew. Chem. 2001, 113, 3382

<A NAME="RA35304ST-66B">66b</A> Bolm C. Rudolph J. J. Am. Chem. Soc. 2002, 124: 14850

<A NAME="RA35304ST-66C">66c</A> Rudolph J. Schmidt F. Bolm C. Adv. Synth. Catal. 2004, 346: 867

For selected APIs, see: (S)-Carbinoxamine:

<A NAME="RA35304ST-67A">67a</A> Roszowski AP. Govier WM. Pharmakologist 1959, 1: 60

<A NAME="RA35304ST-67B">67b</A> Hunt JH. J. Chem. Soc. 1961, 2228

<A NAME="RA35304ST-67C">67c</A> Barouh V. Dall H. Patel D. Hite G. J. Med. Chem. 1971, 14: 834

<A NAME="RA35304ST-67D">67d</A> James MNG. Williams GJB. Can. J. Chem. 1974, 52: 1872

(R)-Neobenodin and (R)-orphenadrin:

<A NAME="RA35304ST-67F">67f</A> Casy AF. Drake AF. Ganellin CR. Mercer AD. Chirality 1992, 4: 356

<A NAME="RA35304ST-67G">67g</A> van der Stelt C. Heus WJ. Nauta WT. Arzneim.-Forsch. 1969, 19: 2010

<A NAME="RA35304ST-67H">67h</A> Rekker RF. Timmerman H. Harms AF. Nauta WT. Arzneim.-Forsch. 1971, 21: 688

<A NAME="RA35304ST-68A">68a</A> Corey EJ. Helal CJ. Tetrahedron Lett. 1995, 36: 9153

<A NAME="RA35304ST-68B">68b</A> Corey EJ. Helal CJ. Tetrahedron Lett. 1996, 37: 4837

<A NAME="RA35304ST-68C">68c</A> Corey EJ. Helal CJ. Tetrahedron Lett. 1996, 37: 5675

<A NAME="RA35304ST-68D">68d</A> Corey EJ. Helal CJ. Angew. Chem. Int. Ed. 1998, 37: 1986 ; Angew. Chem. 1998, 110, 2092

<A NAME="RA35304ST-69A">69a</A> Okhuma T. Koizumi M. Ikehira H. Yokozawa T. Noyori R. Org. Lett. 2000, 2: 659

<A NAME="RA35304ST-69B">69b</A> Noyori R. Okhuma T. Pure Appl. Chem. 1999, 71: 1493

<A NAME="RA35304ST-70">70</A> Hermanns N. PhD Thesis RWTH; Aachen: 2002.

<A NAME="RA35304ST-71">71</A> Rudolph J. PhD Thesis RWTH; Aachen: 2004.

<A NAME="RA35304ST-72A">72a</A> Dahmen S. Bräse S. J. Am. Chem. Soc. 2002, 124: 5940

<A NAME="RA35304ST-72B">72b</A> Hermanns N. Dahmen S. Bolm C. Bräse S. Angew. Chem. Int. Ed. 2002, 41: 3692 ; Angew. Chem. 2002, 114, 3844

Bräse, S.; Dahmen, S.; Vogt, H. to be submitted.

<A NAME="RA35304ST-74">74</A> Knepper K. Ziegert RE. Bräse S. Tetrahedron 2004, 60: 8591