Alcohol Dehydrogenase-Triggered Oxa-Michael Reaction for the Asymmetric Synthesis of Disubstituted Tetrahydropyrans and Tetrahydrofurans
Harry Eastman
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD UK
Search for more papers by this authorCorresponding Author
Dr. James Ryan
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD UK
Search for more papers by this authorDr. Beatriz Maciá
Faculty of Science & Engineering, Division of Chemistry & Environmental Science, Manchester Metropolitan University, Chester Street, Manchester, M1 5GD United Kingdom
Search for more papers by this authorDr. Vittorio Caprio
Faculty of Science & Engineering, Division of Chemistry & Environmental Science, Manchester Metropolitan University, Chester Street, Manchester, M1 5GD United Kingdom
Search for more papers by this authorCorresponding Author
Dr. Elaine O'Reilly
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD UK
Current address: School of Chemistry, University College Dublin, Belfield, Dublin, 4 Ireland
Search for more papers by this authorHarry Eastman
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD UK
Search for more papers by this authorCorresponding Author
Dr. James Ryan
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD UK
Search for more papers by this authorDr. Beatriz Maciá
Faculty of Science & Engineering, Division of Chemistry & Environmental Science, Manchester Metropolitan University, Chester Street, Manchester, M1 5GD United Kingdom
Search for more papers by this authorDr. Vittorio Caprio
Faculty of Science & Engineering, Division of Chemistry & Environmental Science, Manchester Metropolitan University, Chester Street, Manchester, M1 5GD United Kingdom
Search for more papers by this authorCorresponding Author
Dr. Elaine O'Reilly
School of Chemistry, University of Nottingham, University Park, Nottingham, NG7 2RD UK
Current address: School of Chemistry, University College Dublin, Belfield, Dublin, 4 Ireland
Search for more papers by this authorGraphical Abstract
Chemoenzymatic strategy: An alcohol dehydrogenase-triggered asymmetric reduction and subsequent intramolecular oxa-Michael reaction has been developed for the preparation of tetrahydropyrans (or oxanes) and tetrahydrofurans, with excellent conversion, yield and high enantiomeric and diastereomeric excess.
Abstract
An alcohol dehydrogenase-mediated asymmetric reduction and subsequent intramolecular oxa-Michael reaction has been developed for the preparation of tetrahydropyrans (or oxanes) and tetrahydrofurans, in excellent conversion, yield and high enantiomeric and diastereomeric excess. To highlight the utility of the methodology, we report the synthesis of an analogue of the fungal antioxidant brocaketone A. Also described is the preparation of the (–)-(R,R)-enantiomer of the natural product, (+)-(S,S)-(cis-6-methyltetrahydropyran-2-yl)acetic acid.
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References
- 1
- 1aC. F. Nising, S. Brase, Chem. Soc. Rev. 2008, 37, 1218–1228;
- 1bC. F. Nising, S. Brase, Chem. Soc. Rev. 2012, 41, 988–999;
- 1cQ. Dai, N. K. Rana, J. C.-G. Zhao, Org. Lett. 2013, 15, 2922–2925;
- 1dJ. Hu, M. Bian, H. Ding, Tetrahedron Lett. 2016, 57, 5519–5539;
- 1eC. del Pozo, M. Sánchez-Roselló, J. Miró, Synthesis. 2017, 49, 2787–2802. For some other examples on asymmetric synthesis of THPs/THFs see:
- 1fD. S. B. Daniels, A. L. Thompson, E. A. Anderson, Angew. Chem. Int. Ed. 2011, 50, 11506–11510;
Angew. Chem. 2011, 123, 11708–11712
10.1002/ange.201105720 Google Scholar
- 1gB. Mondal, M. Balha, S. Chandra Pan, Asian J. Org. Chem. 2018, 7, 1788–1792. For a further example of the asymmetric synthesis of THPs and a discussion on the mechanism of formation of cis/trans isomers under acidic and basic conditions see:
- 1hH. Fuwa, N. Ichinokawa, K. Noto, M. Sasaki, J. Org. Chem. 2012, 77, 2588–2607.
- 2
- 2aG. S. Rao, N. Sudhakar, B. V. Rao, S. J. Basha, Tetrahedron: Asymmetry 2010, 21, 1963–1970;
- 2bA. M. Shelke, V. Rawat, A. Sudalai, G. Suryavanshi, RSC Adv. 2014, 4, 49770–49774;
- 2cH. Kim, Y. Park, J. Hong, Angew. Chem. 2009, 121, 7713–7717;
10.1002/ange.200903690 Google Scholar
- 2dJ. H. Xie, L. C. Guo, X. H. Yang, L. X. Wang, Q. L. Zhou, Org. Lett. 2012, 14, 4758–4761;
- 2eQ. Dai, N. K. Rana, J. C. Zhao, Org. Lett. 2013, 15, 2922–2925;
- 2fK. Sakurai, M. Sasaki, H. Fuwa, Angew. Chem. Int. Ed. 2018, 57, 5143–5146;
Angew. Chem. 2018, 130, 5237–5240.
10.1002/ange.201801561 Google Scholar
- 3
- 3aE. O'Reilly, N. Turner, Nat. Chem. Biol. 2013, 9, 285–288;
- 3bA. Wells, H.-P. Meyer, ChemCatChem. 2014, 6, 918–920;
- 3cA. P. Green, N. J. Turner, Perspect. Sci. 2016, 9, 42–48;
- 3dM. Honig, P. Sondermann, N. J. Turner, E. M. Carreira, Angew. Chem. Int. Ed. 2017, 56, 8942–8973;
Angew. Chem. 2017, 129, 9068–9100;
10.1002/ange.201612462 Google Scholar
- 3eR. de Souza, L. S. M. Miranda, U. T. Bornscheuer, Chem. Eur. J. 2017, 23, 12040–12063.
- 4J. Ryan, M. Šiaučiulis, A. Gomm, B. Maciá, E. O′Reilly, V. Caprio, J. Am. Chem. Soc. 2016, 138, 15798–15800.
- 5
- 5aW. Kroutil, H. Mang, K. Edegger, K. Faber, Curr. Opin. Chem. Biol. 2004, 8, 120–126;
- 5bC. Wandrey, Chem. Rec. 2004, 4, 254–265;
- 5cK. Goldberg, K. Schroer, S. Lütz, A. Liese, Appl. Microbiol. Biotechnol. 2007, 76, 237–248;
- 5dG. W. Huisman, J. Liang, A. Krebber, Curr. Opin. Chem. Biol. 2010, 14, 122–129;
- 5eF. Hollmann, I. W. C. E. Arends, D. Holtmann, Green Chem. 2011, 13, 2285–2313.
- 6
- 6aW. Kroutil, H. Mang, K. Edegger, K. Faber, Adv. Synth. Catal. 2004, 346, 125–142;
- 6bN. J. Turner, Curr. Opin. Chem. Biol. 2010, 14, 115–121;
- 6cD. Romano, R. Villa, F. Molinari, ChemCatChem, 2012, 4, 739–749;
- 6dJ. Liu, S. Wu, Z. Li, Curr. Opin. Chem. Biol. 2018, 43, 77–86.
- 7
- 7aW. Hummel, Appl. Microbiol. Biotechnol. 1990, 34, 15–19;
- 7bW. Hummel, Biotechnol. Lett. 1990, 12, 403–408;
- 7cC. W. Bradshaw, W. Hummel, C. H. Wong, J. Org. Chem. 1992, 57, 1532–1536;
- 7dJ. Haberland, A. Kriegesmann, E. Wolfram, W. Hummel, A. Liese, Appl. Microbiol. Biotechnol. 2002, 58, 595–599;
- 7eJ. Haberland, W. Hummel, T. Daussmann, A. Liese, Org. Process Res. Dev. 2002, 6, 458–462;
- 7fA. Weckbecker, W. Hummel, Biocatal. Biotransform. 2006, 24, 380–389;
- 7gM. Skoupi, C. Vaxelaire, C. Strohmann, M. Christmann, C. M. Niemeyer, Chem. Eur. J. 2015, 21, 8701–8705.
- 8
- 8aB. Maurer, A. Grieder, W. Thommen, Helv. Chim. Acta. 1979, 62, 44–47;
- 8bB. Maurer, W. Thommen, Helv. Chim. Acta. 1979, 62, 1096–1097.
- 9
- 9aD. J. Dixon, S. V. Ley, E. W. Tate, J. Chem. Soc. Perkin Trans. 1, 2000, 15, 2385–2394;
10.1039/b001243m Google Scholar
- 9bM. Babjak, T. Gracza, Tetrahedron, 2011, 67, 4980–4987;
- 9cX.-H. Yang, K. Wang, S.-F. Zhu, J.-H. Xie, Q.-L. Zhou, J. Am. Chem. Soc. 2014, 136, 50, 17426–17429;
- 9dQ. Ruan, L. Zhou, B. Breit, Catal. Commun. 2014, 53, 87–90;
- 9eE. Keinan, K. K. Seth, R. J. Lamed, J. Am. Chem. Soc. 1986, 108, 3474–3480;
- 9fJ. B. Jones, R. S. Hinks, Can. J. Chem., 1987, 65, 704–707;
- 9gS. Mori, S. Iwamoto, S. Yamauchi, Biosci. Biotechnol. Biochem. 2006, 70, 712–717.
- 10This reaction, as well as the biotransformation of the widely accepted substrate acetophenone, was initially used to determine the selectivity of the enzyme. In both cases, LK-ADH exclusively afforded the (R)-alcohol (see SI for details). Optical rotation values for compounds 3b-d and I-3 were then measured and compared to those reported in the literature. Other assignments were then based on this trend.
- 11P. Zhang, L.-H. Meng, A. Mándi, X.-M. Li, T. Kurtán, B.-G. Wang, RSC Adv. 2015, 5, 39870–39877.
- 12H. Zheng, C. Zhao, B. Fang, P. Jing, J. Yang, X. Xie, X. She, J. Org. Chem. 2012, 77, 5656–5663.
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