Cyclic allylic carbonates as a renewable platform for protecting chemistry in water

Article abstract of DOI:10.1039/c8gc01622d

The present work explores different cyclic allylic carbonates as a potential class of allylcarbamate precursors. The 5-membered carbonate formed a carbamate with very good thermal and pH stability, which could be cleanly deprotected in aqueous solution, in just 30 min with 2 mol% Pd(OAc)₂ as catalyst. The polar nature of the installed motif made it possible to deprotect highly unpolar substrates in water as solvent.

Full text of DOI:10.1039/c8gc01622d

View Article Online
View Journal
Green
Chemistry
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: P. Olsén, J.
Morvan, S. Sawadjoon, A. Shatskiy, E. Johnston and B. Åkermark, Green Chem., 2018, DOI:
10.1039/C8GC01622D.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Volume 18 Number
7 7 April 2016 Pages 1821–2242
Green
Chemistry
Accepted Manuscripts are published online shortly after
Cutting-edge research for a greener sustainable future
www.rsc.org/greenchem
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1463-9262
CRITICAL REVIEW
G. Chatel et al.
Heterogeneous catalytic oxidation for lignin valorization into valuable
chemicals: what results? What limitations? What trends?
rsc.li/green-chem

Please do not adjust margins
Green Chemistry
Page 1 of 6
View Article Online
DOI: 10.1039/C8GC01622D
Green Chemistry
COMMUNICATION
Cyclic Allylic Carbonates as a Renewable platform for Protecting
Chemistry in Water
Peter Olséna*, Jennifer Morvana, Supaporn Sawadjoona, Andrey Shatskiya, Eric V. Johnston b* and
Björn Åkermarka*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
The present work explores different cyclic allylic carbonates as a Cyclic carbonates exist in many different ring-sizes with a vast
potential class of allylcarbamate precursors. The 5-membered array of different functionalities. One useful feature of a ring
carbonate formed a carbamate with very good thermal and pH opening reaction is that it leads to the formation of a
stability which could be cleanly deprotected in aqueous solution, chemically active chain end, which in can be used in further
in just 30 min with 2 mol % Pd(OAc)2 as catalyst. The polar nature chemical reactions. The ring-opening reaction between cyclic
of the installed motif made it possible to deprotect highly unpolar carbonates and amine nucleophiles has been shown to work
substrates in water as solvent
effectively in a wide range of organic solvents and under neat
conditions with many different catalytic systems.5 Our
contribution is that we have shown that it is possible to ring-
open cyclic carbonates selectively with unprotected amino
acids in water.5h This feature and the diversity in accessible
cyclic carbonate motifs provide ample opportunities to
Introduction
The ability to veil and unveil the functional groups of
molecules constitutes a fundamental strategy in organic
synthesis.1 Different protecting groups, with strict and clear
removal boundaries, make it possible to synthesize some of
nature’s macromolecules.2 Similarly, the creation of protecting
groups with functional handles, more commonly referred as
cleavable linkers, permits the introduction of more versatile
functions, ranging from support linkers to highly refined
luminescent probes.3 Although protecting groups are
specifically tailor
a protecting group with the desired
properties.6 The work presented takes a holistic view on the
role and properties of cyclic carbonates, both as precursors
and in the product carbamate.
Results and discussion
indispensable in both chemistry and biology, there are fairly Equilibrium behaviour and its connection to synthesis
few green alternatives.
When installing a protection group originating from a cyclic
precursor it is important that the system only leads to mono-
The question we raised was, if it would be possible to develop addition and avoids oligomerization. The ideal cyclic substrate
a new class of amine protecting groups from a renewable should be thermodynamically stable at standard conditions
origin, which has the potential to be readily cleaved off. Our and form a new thermodynamically stable product upon ring
hypothesis was that a specific alkene functionalized cyclic opening. Generally, five membered cyclic carbonates will be
carbonate could be used to achieve this.
the most thermodynamically stable. However, the equilibrium
between open and closed ring may change with different ring
substituents.7
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please do not adjust margins
Green Chemistry
Page 2 of 6
View Article Online
DOI: 10.1039/C8GC01622D
COMMUNICATION
Journal Name
2 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins
Green Chemistry
Page 3 of 6
View Article Online
DOI: 10.1039/C8GC01622D
Journal Name
COMMUNICATION
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3

Please do not adjust margins
Green Chemistry
Page 4 of 6
View Article Online
DOI: 10.1039/C8GC01622D
COMMUNICATION
Journal Name
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx

Please do not adjust margins
Green Chemistry
Page 5 of 6
View Article Online
DOI: 10.1039/C8GC01622D
Journal Name
COMMUNICATION
3
For examples on linker chemistry see (a) K. S. Lam, M. Lebl
and V. Krchňák, Chem. Rev., 1997, 97, 411–44;. (b) F. Guillier,
D. Orain and M. Bradley, Chem. Rev., 2000, 100, 3859; (c) E.
Green Chem., 2012, 14, 1743; (h)M. Honda, M. Tamura, Y.
Nakagawa, K. Nakao, K. Suzuki and K. Tomishige, J. Catal.,
2014, 318, 95–107.
E. Swayze, Tetrahedron Lett., 1997, 38, 8465–8468; (d) B. 10 (a) R. Hekmatshoar, I. Yavari, Y. S. Beheshtiha and M. M.
Sauerbrei, V. Jungmann and H. Waldmann, Angew. Chem.
Int. Ed., 1998, 37, 1143–1146; (e) Y. Kwon, M. A. Coleman
and J. A. Camarero, Angew. Chem. Int. Ed., 2006, 45, 1726–
1729; (f) N. Kotagiri, D. M. Niedzwiedzki, K. Ohara and S.
Achilefu, Angew. Chem. Int. Ed., 2013, 52, 7756–7760; (g) H.-
Heravi, Monatshelfte fur Chemie, 2001, 691, 689–69; (b) A.
Behr, J. Eilting, K. Irawadi, J. Leschinski and F. Lindner, Green
Chem., 2008, 10, 13–30; (c) N. Sotto, C. Cazorla, C. Villette,
M. Billamboz and C. Len, ACS Sustain. Chem. Eng., 2016, 4,
6996–7003;
Z. He, K.-H. Leung, W. Wang, D. S.-H. Chan, C.-H. Leung and 11 (a) M. L. Bender and W. A. Glasson, J. Am. Chem. Soc., 1959,
D.-L. Ma, Chem. Commun., 2014, 50, 5313–5;
81, 1590–1597; (b) P. Olsén, J. Undin, K. Odelius, H. Keul and
A. C. Albertsson, Biomacromolecules, 2016, 17, 3995–4002;
Biochem., 1986, 156, 220–222; (b) A. S. Galanis, F. Albericio, 12 (a) S. Takahashi, L. A. Cohen, H. K. Miller and E. G. Peake, J.
4
(a) J. V. Staros, R. W. Wright and D. M. Swingle, Anal.
M. Grøtli and M. Grotli, Org. Lett., 2009, 11, 4488–4491; (c)
C. M. Gabriel, M. Keener, F. Gallou and B. H. Lipshutz, Org.
Org. Chem., 1971, 36, 1205–1209; (b) M. E. Jung and G. Piizzi,
Chem. Rev., 2005, 105, 1735–1766;
Lett., 2015, 17, 3968–3971; (d) B. H. Lipshutz, J. Org. Chem., 13 S. Höck, R. Marti, R. Riedl and M. Simeunovic, Chimia. Int. J.
2017, 82, 2806–2816; (e) S. B. Lawrenson, R. Arav and M. Chem., 2010, 64, 200–202.
North, Green Chem., 2017, 19, 1685–1691; (f) M. Cortes- 14 (a) F. Guibe and Y. Saint M’leux, Tetrahedron Lett., 1981, 22
,
Clerget, J.-Y. Berthon, I. Krolikiewicz-Renimel, L.
Chaisemartin and B. H. Lipshutz, Green Chem., 19, 4263–
4267;
3591–3594; (b) J. E. Gómez, W. Guo and A. W. Kleij, Org.
Lett., 2016, 18, 6042–6045; (c) A. Behr and J. Leschinski,
Green Chem., 2009, 11, 609; (d) T. Nishikata and B. H.
5
(a) M. Blain, L. Jean-Gérard, R. Auvergne, D. Benazet, S.
Caillol and B. Andrioletti, Green Chem., 2014, 16, 4286; (b) V.
M. Lombardo, E. A. Dhulst, E. K. Leitsch, N. Wilmot, W. H.
Lipshutz, Org. Lett., 2009, 11, 2377–2379; (e) S. C. Zheng, M.
Zhang and X. M. Zhao, Chem. - A Eur. J., 2014, 20, 7216–
7221.
Heath, A. P. Gies, M. D. Miller, J. M. Torkelson and K. A. 15 (a) G. Tao, L. He, W. Liu, L. Xu, W. Xiong, T. Wang and Y. Kou,
Scheidt, European J. Org. Chem., 2015, 2015, 2791–2795; (c)
W. Guo, J. Gõnzalez-Fabra, N. A. G. Bandeira, C. Bo and A. W.
Kleij, Angew. Chem. Int. Ed., 2015, 54, 11686–11690; (d) S.
Sopeña, V. Laserna, W. Guo, E. Martin, E. C. Escudero-Adán
and A. W. Kleij, Adv. Synth. Catal., 2016, 358, 2172– 2178; (e)
M. Blain, H. Yau, L. Jean-Gérard, R. Auvergne, D. Benazet, P.
R. Schreiner, S. Caillol and B. Andrioletti, ChemSusChem,
Green Chem., 2006, 8, 639; (b) M. Zawadzki, F. A. e Silva, U.
Domańska, J. A. P. Coutinho and S. P. M. Ventura, Green
Chem., 2016, 18, 3527–3536; (c) S. Bhattacharyya and F. U.
Shah, ACS Sustain. Chem. Eng., 2016, 4, 5441–5449; (d) T. A.
Faßbach, N. Gösser, F. O. Sommer, A. Behr, X. Guo, S.
Romanski, D. Leinweber and A. J. Vorholt, Appl. Catal. A
Gen., 2017, 543, 173–179;
2016,
Detrembleur, C. Jérôme and T. Tassaing, RSC Adv., 2017,
18993–19001; (g) A. Cornille, M. Blain, R. Auvergne, B.
Andrioletti, B. Boutevin and S. Caillol, Polym. Chem., 2017,
9, 2269–2272; (f) M. Alves, R. Méreau, B. Grignard, C.
7,
8,
592–604. (h) P. Olsén, M. Oschmann, E. Johnston and B.
Åkermark, Green Chem., 2018, 20, 469-475
(a) S. H. Pyo and R. Hatti-Kaul, Adv. Synth. Catal., 2016, 358,
6
834–839; (b) M. Selva, A. Caretto, M. Noè and A. Perosa,
Org. Biomol. Chem., 2014, 12, 4143; (c) P. Olsén, K. Odelius
and A.-C. Albertsson, Macromolecules, 2014, 47, 6189–6195;
(d) D. Tian, B. Liu, Q. Gan, H. Li and D. J. Darensbourg, ACS
Catal., 2012,
2, 2029–2035.
(a) K. J. Ivin, J. Polym. Sci., Part A Polym. Chem., 2000, 38
2137–2146; (b) A. Duda and S. Penczek, ACS Symp. Ser.,
2000, 160–198; (c) P. Olsén, K. Odelius and A.-C. Albertsson,
Biomacromolecules, 2016, 17, 699–709.
Examples in litterature on applications of the investigated
cyclic carbonates; (a) B. M. Trost and A. Aponick, J. Am.
Chem. Soc., 2006, 128, 3931–3933; (b) B. M. Trost, A.
Aponick and B. N. Stanzl, Chem. - A Eur. J., 2007, 13, 9547–
9560; (c) B. M. Trost, B. M. O’Boyle, W. Torres and M. K.
Ameriks, Chem. - A Eur. J., 2011, 17, 7890–7903; (d) B. M.
Trost, A. C. Burns and T. Tautz, Org. Lett., 2011, 13, 4566–
4569; (e) T. Takata, M. Igarashi and T. Endo, J. Polym. Sci.
Part A Polym. Chem., 1991, 29, 781–784; (f) F. Sanda, T.
Fueki and T. Endo, Macromolecules, 1999, 32, 4220–4224.
7
8
,
9
(a) W. Carothers and F. Natta, J. Am. Chem. Soc., 1930, 52,
314–326; (b) R. A. Braun, J. Org. Chem., 1963, 28, 1383–
1384; (c) P. Olsén, K. Odelius, H. Keul and A.-C. Albertsson,
Macromolecules, 2015, 48, 1703–1710; (d) K. Yamaguchi, K.
Ebitani, T. Yoshida, H. Yoshida and K. Kaneda, J. Am. Chem.
Soc., 1999, 121, 4526–4527; (e) K. Tomishige, H. Yasuda, Y.
Yoshida, M. Nurunnabi, B. Li and K. Kunimori, Green Chem.,
2004, 6, 206; (f) S. Liang, H. Liu, T. Jiang, J. Song, G. Yang and
B. Han, Chem. Commun., 2011, 47, 2131–2133; (g) J. Ma, J.
Song, H. Liu, J. Liu, Z. Zhang, T. Jiang, H. Fan and B. Han,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

Green Chemistry
Page 6 of 6
View Article Online
DOI: 10.1039/C8GC01622D
All in water - functional cyclic carbonates as a versatile and renewable protection/deprotection platform