Communication
Organic & Biomolecular Chemistry
ACS Chem. Biol., 2020, 15, 2331–2337; (f) L. C. Watkins,
W. F. DeGrado and G. A. Voth, J. Am. Chem. Soc., 2020, 142,
17425–17433; (g) M. Côté, J. Misasi, T. Ren, A. Bruchez,
K. Lee, C. M. Filone, L. Hensley, Q. Li, D. Ory, K. Chandran
and J. Cunningham, Nature, 2011, 477, 344–348;
(h) V. V. Bakhonsky, A. A. Pashenko, J. Becker,
H. Hausmann, H. J. De Groot, H. S. Overkleeft, A. A. Fokin
and P. R. Schreiner, Dalton Trans., 2020, 49, 14009–14016;
(i) J. Müller, R. A. Kirschner, J. P. Berndt, T. Wulsdorf,
A. Metz, R. Hrdina, P. R. Schreiner, A. Geyer and G. Klebe,
ChemMedChem, 2019, 14, 663–672.
3 (a) K. A. Agnew-Francis and C. M. Williams, Adv. Synth.
Catal., 2016, 358, 675–700; (b) J.-P. Berndt, Y. Radchenko,
J. Becker, C. Logemann, D. R. Bhandari, R. Hrdina and
P. R. Schreiner, Chem. Sci., 2019, 10, 3324–3329.
4 H. Nasrallah and J.-C. Hierso, Chem. Mater., 2018, 31, 619–
642.
5 A. Štimac, M. Šekutor, K. Mlinarić-Majerski, L. Frkanec and
R. Frkanec, Molecules, 2017, 22, 297.
6 N. Moorthy, V. Poongavanam and V. Pratheepa, Mini-Rev.
Med. Chem., 2014, 14, 819–830.
7 Th. Boehme, K. Ritter, C. Engel, S. Guessregen, T. Haack
and G. Tschank, WO2012120050, 2012.
8 A. G. Moore, S. R. Schow, R. T. Lum, M. G. Nelson and
C. R. Melville, Synthesis, 1999, 1123–1126.
Scheme 2 Oxidation of nordiamantane carbaldehyde 6d to carboxylic
acid 14; X-ray analysis structure of 14 is shown.
Nordiamantane derivative 6d was oxidized to afford the corres-
ponding acid 14 as an example. The reaction proceeded quan-
titatively using oxygen as the oxidant and dipropylene glycol
dimethylether as a solvent.25 The structure of the resulting
nordiamantane carboxylic acid 14 was confirmed by X-ray crys-
tallography (Scheme 2).
To conclude, we have developed a new pathway to norada-
mantane derivatives by decarboxylative ring-contraction of ada-
mantane-based N-methyl carbamates. This method allows the
preparation of known compounds and building blocks,
namely noradamantane carbaldehyde and protoadamanta-
none, and provides access to new compounds, including dia-
mantane-derived hydrocarbon cages.
9 (a) M. Lipsitch, J. B. Plotkin, L. Simonsen and B. Bloom,
Science, 2012, 336, 1529–1531; (b) W. L. Davies,
R. R. Grunert, R. F. Haff, J. W. McGahen, E. M. Neumayer,
M. Paulshock, J. C. Watts, T. R. Wood, E. C. Hermann and
C. E. Hoffmann, Science, 1964, 144, 862–863; (c) P. Camps,
M. D. Duque, S. Vázquez, L. Naesens, E. De Clercq,
F. X. Sureda, M. López-Querol, A. Camins, M. Pallàs,
S. R. Prathalingam, J. M. Kelly, V. Romerof, D. Ivorra and
D. Cortés, Bioorg. Med. Chem., 2008, 16, 9925–9936;
(d) E. Torres, R. Fernandez, S. Miquet, M. Font-Bardia,
E. Vanderlinden, L. Naesens and S. Vazquez, ACS Med.
Chem. Lett., 2012, 3, 1065–1069.
10 (a) V. Pardali, E. Giannakopoulou, A. Konstantinidi,
A. Kolocouris and G. Zoidis, Croat. Chem. Acta, 2019, 92,
211–228; (b) M. Hussain, H. D. Galvin, T. Y. Haw,
A. N. Nutsford and M. Husain, Infect. Drug Resist., 2017, 10,
121.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the DFG (HR 97/1-1). The authors
would like to thank members of the Institute of Organic
Chemistry JLU Giessen for their generous and continuous
support, Lukas Ochmann for synthetic discussions, Dr Heike
Hausmann for NMR experiments, Dr Artur Mardyukov for DFT
analyses and Prof. Pavel Kočovský for manuscript
proofreading.
Notes and references
11 G. Zoidis, N. Kolocouris, L. Naesens and E. De Clercq,
Bioorg. Med. Chem., 2009, 17, 1534–1541.
1 (a) R. C. Fort and P. v. R. Schleyer, Chem. Rev., 1964, 64,
277–300; (b) R. Yasue and K. Yoshida, Adv. Synth. Catal., 12 J. Janjatovic and Z. Majerski, J. Org. Chem., 1980, 45, 4892–
2021, 363, 1662–1671. 4898.
2 (a) T. P. Stockdale and C. M. Williams, Chem. Soc. Rev., 13 M. Eakin, J. Martin and W. Parker, Chem. Commun., 1965,
2015, 44, 7737–7763; (b) L. Wanka, K. Iqbal and 206–206.
P. R. Schreiner, Chem. Rev., 2013, 113, 3516–3604; (c) E. De 14 B. Zonker, E. Duman, H. Hausmann, J. Becker and
Clercq, Nat. Rev. Drug Discovery, 2006, 5, 1015–1025; R. Hrdina, Org. Biomol. Chem., 2020, 18, 4941–4945.
(d) R. Hrdina, F. M. Metz, M. Larrosa, J. P. Berndt, 15 C. Grondal, M. Jeanty and D. Enders, Nat. Chem., 2010, 2,
Y. Y. Zhygadlo, S. Becker and J. Becker, Eur. J. Org. Chem., 167–178.
2015, 6231–6236; (e) C. Tzitzoglaki, K. McGuire, 16 R. Hrdina, M. Larrosa and C. Logemann, J. Org. Chem.,
P. Lagarias, A. Konstantinidi, A. Hoffmann, N. A. Fokina, 2017, 82, 4891–4899.
C. Ma, I. P. Papanastasiou, P. R. Schreiner, S. Vázquez, 17 K. i. Takeuchi, I. Kitagawa, F. Akiyama, T. Shibata, M. Kato
M. Schmidtke, J. Wang, D. D. Busath and A. Kolocouris,
and K. Okamoto, Synthesis, 1987, 612–615.
4030 | Org. Biomol. Chem., 2021, 19, 4027–4031
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