Synthesis 2018; 50(04): 846-852
DOI: 10.1055/s-0036-1591742
paper
© Georg Thieme Verlag Stuttgart · New York

Practical and Scalable Synthesis of 7-Azetidin-1-yl-4-(hydroxy­methyl)coumarin: An Improved Photoremovable Group

Giovanni Bassolino
Laboratorium für Organische Chemie, ETH Zürich, HCI G329, Vladimir-Prelog-Weg 3, 8093 Zürich, Switzerland   eMail: pablo.rivera-fuentes@org.chem.ethz.ch
,
Elias A. Halabi
Laboratorium für Organische Chemie, ETH Zürich, HCI G329, Vladimir-Prelog-Weg 3, 8093 Zürich, Switzerland   eMail: pablo.rivera-fuentes@org.chem.ethz.ch
,
Laboratorium für Organische Chemie, ETH Zürich, HCI G329, Vladimir-Prelog-Weg 3, 8093 Zürich, Switzerland   eMail: pablo.rivera-fuentes@org.chem.ethz.ch
› Institutsangaben
This work was supported by the Swiss National Science Foundation (grant 200021_165551).
Weitere Informationen

Publikationsverlauf

Received: 25. Oktober 2017

Accepted after revision: 27. November 2017

Publikationsdatum:
21. Dezember 2017 (online)


Published as part of the Bürgenstock Special Section 2017 Future­ Stars in Organic Chemistry

Abstract

7-Substituted 4-methylcoumarin derivatives are widely employed as photoprotecting groups in chemistry and biology. We have recently shown that the 7-azetidinylated version of this photocage releases carboxylic acids in aqueous solution more efficiently than the traditionally used 7-diethylamino variant. Here we present a robust and scalable route to prepare the 7-azetidinylated alcohol, a useful precursor for the photoprotection of a variety of leaving groups, and its use in the preparation of model phosphate, sulfonate, and carbamate derivatives.

Supporting Information

 
  • References

  • 1 Valeur B. Berberan-Santos MN. Molecular Fluorescence . Wiley-VCH; Weinheim: 2012: 75-107
  • 2 Lavis LD. Raines RT. ACS Chem. Biol. 2008; 3: 142
  • 3 Klán P. Šolomek T. Bochet CG. Blanc A. Givens R. Rubina M. Popik V. Kostikov A. Wirz J. Chem. Rev. 2013; 113: 119
  • 4 Givens RS. Rubina M. Wirz J. Photochem. Photobiol. Sci. 2012; 11: 472
  • 5 Nadler A. Yushchenko DA. Müller R. Stein F. Feng S. Mulle C. Carta M. Schultz C. Nat. Commun. 2015; 6: 10056
  • 6 Pavlovic I. Thakor DT. Vargas JR. McKinlay CJ. Hauke S. Anstaett P. Camuña RC. Bigler L. Gasser G. Schultz C. Wender PA. Jessen HJ. Nat. Commun. 2016; 7: 10622
  • 7 Weis S. Shafiq Z. Gropeanu RA. del Campo A. J. Photochem. Photobiol., A 2012; 241: 52
  • 8 Maddipatla MV. S. N. Wehrung D. Tang C. Fan W. Oyewumi MO. Miyoshi T. Joy A. Macromolecules 2013; 46: 5133
  • 9 San Miguel V. Bochet CG. del Campo A. J. Am. Chem. Soc. 2011; 133: 5380
  • 10 Shembekar VR. Chen Y. Carpenter BK. Hess GP. Biochemistry 2007; 46: 5479
  • 11 Suzuki AZ. Watanabe T. Kawamoto M. Nishiyama K. Yamashita H. Ishii M. Iwamura M. Furuta T. Org. Lett. 2003; 5: 4867
  • 12 Schmidt R. Geissler D. Hagen V. Bendig J. J. Phys. Chem. A 2007; 111: 5768
  • 13 Pinheiro AV. Baptista P. Lima JC. Nucleic Acids Res. 2008; 36: e90
  • 14 Shembekar VR. Chen Y. Carpenter BK. Hess GP. Biochemistry 2005; 44: 7107
  • 15 Schönleber RO. Bendig J. Hagen V. Giese B. Bioorg. Med. Chem. 2002; 10: 97
  • 16 Cürten B. Kullmann PH. M. Bier ME. Kandler K. Schmidt BF. Photochem. Photobiol. 2005; 81: 641
  • 17 Grimm JB. English BP. Chen J. Slaughter JP. Zhang Z. Revyakin A. Patel R. Macklin JJ. Normanno D. Singer RH. Lionnet T. Lavis LD. Nat. Methods 2015; 12: 244
  • 18 Liu X. Qiao Q. Tian W. Liu W. Chen J. Lang MJ. Xu Z. J. Am. Chem. Soc. 2016; 138: 6960
  • 19 Bassolino G. Nançoz C. Thiel Z. Bois E. Vauthey E. Rivera-Fuentes P. Chem. Sci. 2018; in press; DOI: 10.1039/c7sc03627b
  • 20 Geißler D. Antonenko YN. Schmidt R. Keller S. Krylova OO. Wiesner B. Bendig J. Pohl P. Hagen V. Angew. Chem. Int. Ed. 2005; 44: 1195
  • 21 Skwarczynski M. Noguchi M. Hirota S. Sohma Y. Kimura T. Hayashi Y. Kiso Y. Bioorg. Med. Chem. Lett. 2006; 16: 4492
  • 22 Abraham J. Mankoci S. Chamsaz EA. US Patent Appl. No. 15/383144, 2017
  • 23 Sharghi H. Jokar M. Heterocycles 2007; 71: 2721
  • 24 Zhou Z. Fahrni CJ. J. Am. Chem. Soc. 2004; 126: 8862
  • 25 Kozlowski J. Coburn C. Yu W. Tong L. Hu B. Zhong B. Hao J. Wang D. Tao J. WO 2015/094998 A1, 2015
  • 26 Li X. Reuman M. Russell RK. Adams R. Ma R. Beish S. Branum S. Youells S. Roberts J. Jain N. Kanojia R. Sui Z. Org. Process Res. Dev. 2007; 11: 414
  • 27 Kanojia RM. Jain N. Xu J. Sui Z. Tetrahedron Lett. 2004; 45: 5837
  • 28 Chen N. Jain N. Xu J. Reuman M. Li X. Russell RK. Sui Z. Tetrahedron Lett. 2006; 47: 5909
  • 29 Zhang X. Sui Z. Synthesis 2006; 2568
  • 30 Mazunin D. Dissertation. ETH Zürich; Switzerland: 2016. Dissertation No. 2356
  • 31 Wirtz L. Kazmaier U. Eur. J. Org. Chem. 2011; 7062
  • 32 Piloto AM. Hungerford G. Costa SP. G. Gonçalves MS. T. Eur. J. Org. Chem. 2013; 7715
  • 33 Piloto AM. Hungerford G. Sutter JU. Soares AM. S. Costa SP. G. Gonçalves MS. T. J. Photochem. Photobiol., A 2015; 299: 44
  • 34 ThermoFisher Scientific, 10010 - PBS, pH 7.4; see: http://www.thermofisher.com/ch/en/home/technical-resources/ media-formulation.160.html (accessed 14.09.2017).
  • 35 Ramnial T. Taylor SA. Bender ML. Gorodetsky B. Lee PT. K. Dickie DA. McCollum BM. Pye CC. Walsby CJ. Clyburne JA. C. J. Org. Chem. 2008; 73: 801