Theoretical studies on enantioselective reduction of ketone with borane catalyzed by a B-methoxy-oxazaborolidine catalyst derived from pinene have been performed by means of the density functional theory (DFT) method. All the structures were optimized completely using wB97XD/6-31G(d,p) level and the mechanism of the enantioselective reduction is studied. The formation of the M4s complexes via transition state TS3s was the rate-determining step and the chirality-limiting step for this enantioselective reduction; the dominant reaction is the attack of proton from the Si surface of M3a, which provides the corresponding secondary alcohols in 98% ee. NCI analysis of the four computed transition states associated with stereoselectivity-determining step discloses that TS3a(S) is the stable conformation with respect to TS3a(R), TS3b(S), and TS3b(R). The produced reaction pathway takes place through: M1 → M2a → M3a → M4a(S) → M5a(S) → M6a(S) → M7a(S). The chirality of the reduced product is of S type, which is in agreement with the experiment.
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Hirao A, Itsuno S, Nakahama S, Yamazaki N (1981). J Chem Soc Chem Commun 0:315–317
Hirao A, Itsuno S, Nakahama S, Ito K (1983). J Chem Soc Chem Commun 0:469–470.S
Corey EJ, Bakshi RK, Shibata S (1987). J Am Chem Soc 109:5551
Corey EJ, Bakshi RK, Shibata S, Chen CP, Singh VK (1987). J Am Chem Soc 109:7925–7926
Corey EJ, Shibata S, Bakshi RK (1988). J Org Chem 53:2861
Corey EJ, Helal CJ (1998). Angew Chem Int Ed 37:1986–2012
Wallbaum S, Martens J (1992). Tetrahedron Asym 3:1475–1504
Singh VK (1992). Synthesis:605
Deloux L, Srebnik M (1993). Chem Rev 93:763
Corey EJ, Helal CJ (1998). Angew Chem Int Ed Engl 37:1986
Liu H, Xu JXJ (2006). Mol Catal A Chem 244:68–72
Xu J, Wei T, Zhang Q (2004). J Org Chem 69:6860–6866
Garrett CE, Prasad K, Repic O, Blacklock TJ (2002). Tetrahedron Asymm 13:1347–1349
Cho BT (2006). Tetrahedron 62:7621–7643
Glushkov VA, Tolstikov AG (2004). Russ Chem Rev 73:581–608
Masui M, Shioiri T (1997). Synlett:273–274
Dennis H, Baro A, Laschat S, Frey W (2008). Tetrahedron 64:1635–1640
Wei D, Tang M, Zhao J, Sun L, Zhang W, Zhao C, Zhang S, Wang H (2009). Tetrahedron Asym 20:1020–1026
Krzemiński MP, Wojtczak A (1996). Tetrahedron Lett 37:7131–7134
Frisch MJ (2009) Gaussian 09, Revision A.02. Gaussian, Wallingford, CT
Zhao Y, Truhlar DG (2004). J Phys Chem A 108:6908
Hehre WJ, Radom L, Schleyer PVR, Pople JA (1986) Ab initio molecular orbital theory. Wiley, New York
Gonzalez C, Schlegel HB (1990). J Phys Chem 94:5523–5527
Gonzalez C, Schlegel HB (1989). J Chem Phys 90:2154–2161
Łączkowski KZ, Czyżnikowska Ż, Zaleśny R, Baranowska-Łączkowska A (2013). Struct Chem 24:485–1492
Ujaque G, Lee PS, Houk KN, Hentemann MF, Danishefsky SJ (2002). Chem Eur J 8:3423
Johnson ER, Keinan S, Mori-Sanchez P, Contreras-Garcia J, Cohen J, Yang AW (2010). J Am Chem Soc 132:6498
I am grateful to Doctor Abdelmalek Khorief Nacereddine (Université Badji Mokhtar Annaba) for helpful discussion.
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Kettouche, H.S. A DFT study on the reaction mechanism of enantioselective reduction of ketones with borane catalyzed by a B-methoxy-oxazaborolidine catalyst derived from (–)-β-pinene. J Mol Model 26, 27 (2020) doi:10.1007/s00894-019-4276-0
- Transition state
- Enantioselective reduction