Chiral 1,4-Hydroxyarylalcohols (HAROLs) and 1,4-Aminoalkylphenols (AAPs) as Organocatalysts for Asymmetric Hetero Diels-Alder Reaction

Year 2019, Volume: 14 Issue: 2, 436 - 441, 30.11.2019

Erkan Ertürk , Mustafa Ali Tezeren Tahir Tilki

https://doi.org/10.29233/sdufeffd.649920

Abstract

In this study, two chiral 2-(2-hydroxyaryl) alcohols (HAROLs;
1,4-diols) and a 1,4-aminoalkylphenol (AAP) were examined as hydrogen-bond
donor (HBD) organocatalysts in the asymmetric hetero Diels-Alder (HDA) reaction
of aldehydes with Rawal’s diene. Catalytic
amount (10 mol%) of the both scaffolds (HAROL and AAP) have been found to
effect the HDA reaction in a quite efficient manner. Among them, a HAROL molecule based on indan backbone was turned
out to be the best in terms of catalytic activity and enantioselectivity. On the other hand, AAP tested seemed
to act as a bifunctional organocatalyst, i.e. as both a Lewis base and HBD organocatalyst. Experimental results underpins that a
careful tuning of HAROL structure might lead to the development of more general
HBD organocatalysts.

Keywords

Asymmetric catalysis, Hydrogen-bond donor organocatalyst, Diols, Aminoalkylphenols, Hetero Diels-Alder reaction

Supporting Institution

TÜBİTAK ARDEB ve Süleyman Demirel Üniversitesi BAP

Project Number

TÜBİTAK Proje No: 111T597, Süleyman Demirel Üniversitesi BAP Proje No: 4072-D1-14

Thanks

We would like to thank both the Scientific and Technological Research Council of Turkey (grant no. 111T597) and Süleyman Demirel University (BAP project no. 4072-D1-14) for their financial supports.

Asimetrik Hetero Diels-Alder Reaksiyonu için Organaokatalizör Olarak Kiral 1,4-Hidroksiarilalkoller (HAROL) ve 1,4-Aminoalkilfenoller (AAP)

Abstract

Bu çalışmada, iki tane kiral 2-(2-hidroksiaril) alkol (HAROL, 1,4-diol) ve bir 1,4-aminoalkilfenol (AAP), aldehitlerin Rawal dieni ile asimetrik hetero Diels-Alder (HDA) reaksiyonunda hidrojen-bağı donörü (HBD) organokatalizörleri olarak incelenmiştir. Her iki yapının (HAROL ve AAP) katalitik miktarının (%10) HDA reaksiyonunu oldukça verimli bir şekilde gerçekleştirdiği bulunmuştur. Bunlar arasında, indan iskeleti bazlı bir HAROL molekülünün, katalitik aktivite ve enantioseçicilik bakımından en iyisi olduğu ortaya çıkmıştır. Öte yandan, test edilen AAP bifonksiyonlu bir organokatalizör olarak, diğer bir deyişle bir Lewis bazı ve HBD organokatalizörü gibi davranıyor görünmektedir. Deneysel sonuçlar HAROL yapısının dikkatli bir şekilde ayarlanmasının, daha genel HBD organokatalizörlerinin geliştirilmesine yol açabileceğini desteklemektedir.Bu çalışmada, iki tane kiral 2-(2-hidroksiaril) alkol (HAROL, 1,4-diol) ve bir 1,4-aminoalkilfenol (AAP), aldehitlerin Rawal dieni ile asimetrik hetero Diels-Alder (HDA) reaksiyonunda hidrojen-bağı donörü (HBD) organokatalizörleri olarak incelenmiştir. Her iki yapının (HAROL ve AAP) katalitik miktarının (%10) HDA reaksiyonunu oldukça verimli bir şekilde gerçekleştirdiği bulunmuştur. Bunlar arasında, indan iskeleti bazlı bir HAROL molekülünün, katalitik aktivite ve enantioseçicilik bakımından en iyisi olduğu ortaya çıkmıştır. Öte yandan, test edilen AAP bifonksiyonlu bir organokatalizör olarak, diğer bir deyişle bir Lewis bazı ve HBD organokatalizörü gibi davranıyor görünmektedir. Deneysel sonuçlar HAROL yapısının dikkatli bir şekilde ayarlanmasının, daha genel HBD organokatalizörlerinin geliştirilmesine yol açabileceğini desteklemektedir.

Keywords

Asimetrik kataliz, Hidrojen bağı sağlayıcı organokatalizör, Dioller, Aminoalkilfenoller, Hetero Diels-Alder reaksiyonu

Project Number

TÜBİTAK Proje No: 111T597, Süleyman Demirel Üniversitesi BAP Proje No: 4072-D1-14

References

• [1] K. A. Jorgensen, “Catalytic asymmetric hetero-Diels-Alder reactions of carbonyl compounds and imines,” Angew. Chem. Int. Ed., 39, 3558–3588, 2000.
• [2] H. Pellissier, “Asymmetric hetero-Diels-Alder reactions of carbonyl compounds,” Tetrahedron, 65, 2839–2877, 2009.
• [3] G. Blond, M. Gulea, and V. Mamane, “Recent contributions to hetero Diels-Alder reactions,” Curr. Org. Chem., 20, 2161–2210, 2016.
• [4] A. Berkessel and H. Gröger, Asymmetric Organocatalysis. Weinheim: Wiley-VCH, 2005.
• [5] M. S. Taylor and E. N. Jacobsen, “Asymmetric catalysis by chiral hydrogen-bond donors,” Angew. Chem. Int. Ed., 45, 1520–1543, 2006.
• [6] T. N. Nguyen, P.-A. Chen, K. Setthakarn, and J. A. May, “Chiral diol-based organocatalysts in enantioselective reactions,” Molecules, 23, 2317–2353, 2018.
• [7] A. Berkessel, S. S. Vormittag, N. E. Schlörer, and J.-M. Neudörfl, “TEFDDOLs (α,α,α′,α′-tetrakis(perfluoroaryl/alkyl)-2,2′-dimethyl-1,3-dioxolane-4,5-dimethanols): Highly fluorinated chiral H-bond donors and Brønsted acids with distinct H-bonding patterns and supramolecular architectures,” J. Org. Chem., 77, 10145–10157, 2012.
• [8] V. H. Rawal, A. N. Thadani, A. K. Unni, and Y. Huang, “Single enantiomers from a chiral-alcohol catalyst,” Nature, 424, 146, 2003.
• [9] A. K. Unni, N. Takenaka, H. Yamamoto, and V. H. Rawal, “Axially chiral biaryl diols catalyze highly enantioselective hetero-Diels-Alder reactions through hydrogen bonding,” J. Am. Chem. Soc., 127, 1336–1337, 2005.
• [10] H. Du, D. Zhao, and K. Ding, “Enantioselective catalysis of the hetero-Diels-Alder reaction between Brassard’s diene and aldehydes by hydrogen-bonding activation: A one-step synthesis of (S)-(+)-dihydrokawain,” Chem. Eur. J., 10, 5964–5970, 2004.
• [11] X. Zhang, H. Du, Z. Wang, Y.-D. Wu, and K. Ding, “Experimental and theoretical studies on the hydrogen-bond-promoted enantioselective hetero-Diels-Alder reaction of Danishefsky’s diene with benzaldehyde,” J. Org. Chem., 71, 2862–2869, 2006.
• [12] C. Beemelmanns, R. Husmann, D. K. Whelligan, S. Özçubukçu, and C. Bolm, “Planar-chiral bis-silanols and diols as H-bonding asymmetric organocatalysts,” Eur. J. Org. Chem., 3373–3376, 2012.
• [13] C. Nottingham, H. Müller-Bunz, and P. J. Guiry, “A family of chiral ferrocenyl diols: Modular synthesis, solid-state characterization, and application in asymmetric organocatalysis,” Angew. Chem. Int. Ed., 55, 11115–11119, 2016.
• [14] T. Kanemitsu, Y. Asajima, T. Shibata, M. Miyazaki, K. Nagata, and T. Itoh, “Novel sulfonamide catalyzed asymmetric hetero Diels-Alder reaction of ethyl glyoxylate with Danishefsky’s diene,” Heterocycles, 83, 2525–2534, 2011.
• [15] J. Hine, S.-M. Linden, and V. M. Kanagasabapathy, “1,8-Biphenylenediol is a double-hydrogen-bonding catalyst for reaction of an epoxide with a nucleophile,” J. Am. Chem. Soc., 107, 1082–1083, 1985.
• [16] Y. E. Türkmen and V. H. Rawal, “Exploring the potential of diarylacetylenediols as hydrogen bonding catalysts,” J. Org. Chem., 78, 8340–8353, 2013.
• [17] P. Chauhan and S. S. Chimni, “Aromatic hydroxyl group - a hydrogen bonding activator in bifunctional asymmetric organocatalysis,” RSC Adv., 2, 737–758, 2012.
• [18] E. Ertürk, M. A. Tezeren, T. Atalar, and T. Tilki, “Regioselective ring-opening of epoxides with ortho-lithioanisoles catalyzed by BF3·OEt2,” Tetrahedron, 68, 6463–6471, 2012.
• [19] Ö. Dilek, M. A. Tezeren, T. Tilki, and E. Ertürk, “Chiral 2-(2-hydroxyaryl)alcohols (HAROLs) with a 1,4-diol ccaffold as a new family of ligands and organocatalysts,” Tetrahedron, 74, 268–286, 2018.
• [20] M. A. Tezeren, T. A. Yeşil, Y. Zorlu, T. Tilki, and E. Ertürk, “Enantiopure cis-and trans-2-(2-aminocyclohexyl)phenols: Effective preparation, solid-state characterization, and application in asymmetric organocatalysis,” Eur. J. Org. Chem., 7017–7032, 2018.
• [21] Ö. Dilek, M. A. Tezeren, T. Tilki, and E. Ertürk, “Chiral 1,4-aminoalkylphenols for enantioselective diethylzinc addition to aldehydes,” Turk. J. Chem., 43, 612–623, 2019.