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Kinetic Separation of cis- and trans-Limonene Epoxide: Reaction of Diastereomeric Mixture of Limonene Oxides with Secondary Amine and Carbamate
Corresponding Author(s) : M.M. El Hammoumi
Asian Journal of Chemistry,
Vol. 33 No. 11 (2021): Vol 33 Issue 11, 2021
Abstract
A simple kinetic separation of (1:1) diastereomeric mixture of limonene oxides was used to purify cis- and trans-diastereomers of (R)-(+)-limonene oxide. The epoxide ring of trans-isomer was selectively opened by (R)-N-methyl-(α-methyl-benzyl)amine. This secondary nucleophilic amine left cis-limonene oxide largely unreacted and was obtained up to 90% yield. In a diverse way, (R)-N-(α-methyl-benzyl) ethyl carbamate, selectively catalyze hydrolysis of cis-limonene oxide to 1,2-limonene diol leaving trans-limonene oxide largely unreacted. The unreacted trans-limonene oxide was recovered in up to 75% yield. HPLC and NMR analyses were used to demonstrate that the isolation of cis- and trans-diastereomers of (R)-(+)-limonene oxide has shown that > 98% were pure. As a result, depending on the realization of the secondary amine or carbamate in the presence of water, either cis- or trans-limonene oxide may be obtained in high diastereomeric purity.
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References
S. Meninno and A. Lattanzi, Chem. Eur. J., 22, 3632 (2016); https://doi.org/10.1002/chem.201504226
Y. Zhu, Q. Wang, R.G. Cornwall and Y. Shi, Chem. Rev., 114, 8199 (2014); https://doi.org/10.1021/cr500064w
L. Kiss, A.M. Remete, M. Nonn, S. Fustero, R. Sillanpaa and F. Fülöp, Tetrahedron, 72, 781 (2016); https://doi.org/10.1016/j.tet.2015.12.017
L. Kiss, E. Forró and F. Fülöp, Tetrahedron, 68, 4438 (2012); https://doi.org/10.1016/j.tet.2011.12.065
P.A. Wang, Beilstein J. Org. Chem., 9, 1677 (2013); https://doi.org/10.3762/bjoc.9.192
E.J. de Vries and D.B. Janssen, Curr. Opin. Biotechnol., 14, 414 (2003); https://doi.org/10.1016/s0958-1669(03)00102-2
I.M. Figueiredo, L.V. Santos, W.F. Costa, J.E. Carvalho, C.C. Silva, J.L. Sacoman, K.L. Kohn and M.H. Sarragiotto, J. Braz. Chem. Soc., 17, 954 (2006); https://doi.org/10.1590/S0103-50532006000500020
S.R. Ferrarini, C.S. Graebin, J. Limberger, R.F.S. Canto, D.O. Dias, R.G. da Rosa, M. de F. Madeira and V.L. Eifler-Lima, Mem. Inst. Oswaldo Cruz, 103, 773 (2008); https://doi.org/10.1590/S0074-02762008000800005
D. Steiner, L. Ivison, C.T. Goralski, R.B. Appell, J.R. Gojkovic and B. Singaram, Tetrahedron Asym., 13, 2359 (2002); https://doi.org/10.1016/S0957-4166(02)00646-8
M. Blair, P.C. Andrews, B. H. Fraser, C. M. Forsyth, P. C. Junk, M. Massi, K.L. Tuck, Synthesis, 1523 (2007); https://doi.org/10.1055/S-2007-966033
S.C. Santosh Kumar, J.R. Manjunatha, P. Srinivas and B.K. Bettadaiah, J. Chem. Sci., 126, 875 (2014); https://doi.org/10.1007/s12039-014-0633-9
L.A. Said, M.M. El Hammoumi, C. El Haimer, A. El Bachiri and M. Khoukhi, J. Mol. Struct., 1241, 130691 (2021); https://doi.org/10.1016/j.molstruc.2021.130691
Z.-B. Xu and J. Qu, Chin. J. Chem., 30, 1133 (2012); https://doi.org/10.1002/cjoc.201100455
J.T. Suri, T. Vu, A. Hernandez, J. Congdon and B. Singaram, Tetrahedron Lett., 43, 3649 (2002); https://doi.org/10.1016/S0040-4039(02)00652-4
C. T. Goralski, B. Singaram and W. Chrisman, Chiral Amino Alcohols and Process for Preparation of Same, US Patent 6,362,373 (2002).
B. Singaram, W. Chrisman and C.T. Goralski, World Patent WO 02/22550 (2002).
W. Chrisman, J.N. Camara, K. Marcellini, B. Singaram, C.T. Goralski, D.L. Hasha, P.R. Rudolf, L.W. Nicholson and K.K. Borodychuk, Tetrahedron Lett., 42, 5805 (2001); https://doi.org/10.1016/S0040-4039(01)01135-2
J.C. Leffingwell and E.E. Royals, Tetrahedron Lett., 6, 3829 (1965); https://doi.org/10.1016/S0040-4039(01)89133-4