Abstract
The effect of chiral phosphine ligands PR1R2R3 (R1, R2, R3 = Me, Pri, Bui, p-Tol, cyclohexyl, Ph) on the enantioselectivity of Pd-catalyzed allylation of norbornadiene (NBD) was modeled within the framework of the scalar-relativistic approximation of the density functional theory using the ωB97X-D3(BJ) functional. According to calculations, the reaction in the presence of phosphines PPh(Bui)(Pri), PPh(Pri)Me, and P(Bui)(Pri)Me can proceed regioselectively with respect to exo-products. In all cases, calculations predict the predominance of one of the enantiomers of the exo-product. The highest enantiomeric excess (96%) can be achieved using PPh(Pri)Me.
References
M. Catellani, G. Chiusoli, E. Dradi, G. Salerno, J. Organomet. Chem., 1979, 177, 29; DOI: https://doi.org/10.1016/S0022-328X(00)94094-4.
U. M. Dzhemilev, R. I. Khusnutdinov, G. A. Tolstikov, Russ. Chem. Rev., 1987, 56, 36; DOI: https://doi.org/10.1070/RC1987v056n01ABEH003255.
U. M. Dzhemilev, R. I. Khusnutdinov, D. K. Galeev, O. M. Nefedov, G. A. Tolstikov, Bull. Acad. Sci. USSR, Div. Chem. Sci., 1987, 36, 122; DOI: https://doi.org/10.1007/BF00953861.
I. P. Stolyarov, A. E. Gekhman, I. I. Moiseev, A. Yu. Kolesnikov, E. M. Evstigneeva, V. R. Flid, Russ. Chem. Bull., 2007, 56, 320; DOI: https://doi.org/10.1007/s11172-007-0052-x.
S. A. Durakov, A. A. Kolobov, V. R. Flid, Fine Chem. Technol. (Engl. Transl.), 2022, 17, No. 4, 275; DOI: https://doi.org/10.32362/2410-6593-2022-17-4-275-297.
K. T. Egiazaryan, R. S. Shamsiev, V. R. Flid, Fine Chem. Technologies (Engl. Transl.), 2019, 14, No. 6, 56; DOI: https://doi.org/10.32362/2410-6593-2019-14-6-56-65.
R. S. Shamsiev, K. T. Egiazaryan, V. R. Flid, Russ. Chem. Bull., 2021, 70, 316; DOI: https://doi.org/10.1007/s11172-021-3087-5.
R. S. Shamsiev, K. T. Egiazaryan, V. R. Flid, Russ. Chem. Bull., 2022, 71, 905; DOI: https://doi.org/10.1007/s11172-022-3489-z.
S. A. Durakov, R. S. Shamsiev, V. R. Flid, Russ. Chem. Bull., 2021, 70, 1290; DOI: https://doi.org/10.1007/s11172-021-3213-4.
S. A. Durakov, P. V. Melnikov, E. M. Martsinkevich, A. A. Smirnova, R. S. Shamsiev, V. R. Flid, Russ. Chem. Bull., 2021, 70, 113; DOI: https://doi.org/10.1007/s11172-021-3064-z.
E. H. Krenske, K. N. Houk, Acc. Chem. Res., 2013, 46, 979; DOI: https://doi.org/10.1021/ar3000794.
D. N. Laikov, Chem. Phys. Lett., 1997, 281, 151; DOI: https://doi.org/10.1016/S0009-2614(97)01206-2.
D. N. Laikov, Yu. A. Ustynyuk, Russ. Chem. Bull., 2005, 54, 820; DOI: https://doi.org/10.1007/s11172-005-0329-x.
F. Neese, WIREs Comput. Mol. Sci., 2012, 2, 73; DOI: https://doi.org/10.1002/wcms.8.
F. Neese, WIREs Comput. Mol. Sci., 2017, 7, e1327; DOI: https://doi.org/10.1002/wcms.1327.
J. P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett., 1996, 77, 3865; DOI: https://doi.org/10.1103/PhysRevLett.77.3865.
D. N. Laikov, Chem. Phys. Lett., 2005, 416, 116; DOI: https://doi.org/10.1016/j.cplett.2005.09.046.
R. S. Shamsiev, V. R. Flid, Russ. Chem. Bull., 2013, 62, 2301; DOI: https://doi.org/10.1007/s11172-013-0333-5.
D. V. Dmitriev, R. S. Shamsiev, Ha Ngok Thien, V. R. Flid, Russ. Chem. Bull., 2013, 62, 2385; DOI: https://doi.org/10.1007/s11172-013-0345-1.
A. Najibi, L. Goerigk, J. Chem. Theory Comput., 2018, 14, 5725; DOI: https://doi.org/10.1021/acs.jctc.8b00842.
D. A. Pantazis, Xian-Yang Chen, C. R. Landis, F. Neese, J. Chem. Theory Comput., 2008, 4, 908; DOI: https://doi.org/10.1021/ct800047t.
J. D. Rolfes, F. Neese, D. A. Pantazis, J. Comput. Chem., 2020, 41, 1842; DOI: https://doi.org/10.1002/jcc.26355.
A. V. Marenich, C. J. Cramer, D. G. Truhlar, J. Phys. Chem. B, 2009, 113, 6378; DOI: https://doi.org/10.1021/jp810292n.
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Dedicated to Academician of the Russian Academy of Sciences I. P. Beletskaya on the occasion of her anniversary.
This work was financially supported by the MIREA — Russian Technological University within the framework of a grant for young scientists.
No human or animal subjects were used in this research.
The authors declare no competing interests.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, Vol. 72, No. 4, pp. 838–846, April, 2023.
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Egiazaryan, K.T., Shamsiev, R.S. & Flid, V.R. Enantioselectivity of norbornadiene allylation in the presence of Pd phosphine complexes: a quantum chemical prediction. Russ Chem Bull 72, 838–846 (2023). https://doi.org/10.1007/s11172-023-3847-2
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DOI: https://doi.org/10.1007/s11172-023-3847-2