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Quantum chemical study on asymmetric allylation of benzaldehyde in the presence of chiral allylboronate

  • Materials and Chemical Engineering
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Abstract

The quantum chemical method is employed to study the modified asymmetric allylation of benzaldehyde controlled by diisopropyl D-(−)-tartrate auxiliary. All the structures are optimized completely at the B3LYP/6-31G(d,p) level. The (R)-secondary alcohol can be achieved mainly through a six-membered ring chair-like transition state structure. From the relative reaction rates theory the main product configuration predicted is in agreement with the experiment result.

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References

  • Brown, H.C., Randad, R.S., Bhat, K.S., Zaidlewicz, M., Racherla, U.S., 1990. Chiral synthesis via organoboranes. 24. B-allylbis(2-isocaranyl)borane as a superior reagent for the asymmetric allylboration of aldehydes.J Am Chem. Soc.,112:2389–2392.

    Article  CAS  Google Scholar 

  • Dewar, M.J.S., Reynolds, C.H., 1986. An improved set of MNDO parameters for sulfur.J. Comp. Chem.,2:140–143.

    Article  Google Scholar 

  • Dewar, M.J.S., Zoebisch, E.G., Healy, E.F., 1985. Development and use of quantum mechanical molecular models. 76. AM1: A new general purpose quantum mechanical molecular model.J. Am. Chem. Soc.,107:3902–3909.

    Article  CAS  Google Scholar 

  • Frisch, M.J.G., Trucks, W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Zakrzewski, V.G., Montgomery, J.A., Stratmann, R.E., Burant, J.C.,et al., 1998. Gaussian 98 (Revision A.1). Gaussian, Inc., Pittsburgh PA.

    Google Scholar 

  • Gung, B.W., Xue, X.X., Roush, W.R., 2002. The origin of diastereofacial control in allylboration reaction using tartrate ester derived allylboronates: Attractive interactions between the lewis acid coordinated aldehyde carbonyl group and ester carbonyl oxygen.J. Am. Chem. Soc.,124:10692–10697.

    Article  CAS  Google Scholar 

  • Haruta, R., Ishiguro, M., Ikeda, N., Yamamoto, H., 1982. Chiral allenylboronic esters: A practical reagent for enantioselective carbon-carbon bond formation.J. Am. Chem. Soc.,104:7667–7669.

    Article  CAS  Google Scholar 

  • Jadhav, P.K., Bhat, K.S., Perumal, P.T., Brown, H.C., 1986. Chiral synthesis via organoboranes. 6. Asymmetric allylboration via chiral allyldialkylboranes. Synthesis of homoallylic alcohols with exceptionally high enantiomeric excess.J. Org. Chem.,51:432–439.

    Article  CAS  Google Scholar 

  • Lee, C., Yang, W., Parr, R.G., 1988. Development of the colle-salvetti correlation-energy formula into a functional of the electron density.Physical Review B,37:785–789.

    Article  CAS  Google Scholar 

  • Miehlich, B., Savin, A., Stoll, H., Preuss, H., 1989. Results obtained with the correlation energy density functionals of Becke and Lee-Yang and Parr.Chem. Phys. Lett.,157:200–206.

    Article  CAS  Google Scholar 

  • Racherla, U., Brown, H., 1991. Chiral synthesis via organoboranes. 27. Remarkably rapid and exceptionally enantioselective (approaching 100%e.e.) allylboration of representative aldehydes at −100 degree under new, salt-free conditions.J. Org. Chem.,56:401–404.

    Article  CAS  Google Scholar 

  • Roush, W.R., Adam, M.A., Harris, D.J., 1985a. Stereochemistry of crotylboronate additions to alpha-, beta-dialkoxy aldehydes.J. Org. Chem.,50:2000–2003.

    Article  CAS  Google Scholar 

  • Roush, W.R., Walts, A.E., Hoong, L.K., 1985b. Diastereo- and enantioselective aldehyde addition reactions of 2-allyl-1,3,2-dioxaborolane-4,5-dicarboxylic esters, a useful class of tartrate ester modified allylboronates.J. Am. Chem. Soc.,107:8186–8190.

    Article  CAS  Google Scholar 

  • Roush, W.R., Ando, K., Powers, D.B., Halterman, R.L., Palkowitz, A.D., 1988. Enantioselective synthesis using diisopropyl tartrate modified (E)- and (Z)-crotylboronates: Reaction with achiral aldehyde.Tetrahedron Lett.,29:5579–5582.

    Article  CAS  Google Scholar 

  • Roush, W.R., Hoong, L.K., Palmer, M.A.J., Park, J.C., 1990a. Asymmetric synthesis using tartrate ester modified allylboronates. 1. Factors influencing stereoselectivity.J. Org. Chem.,55:4109–4117.

    Article  CAS  Google Scholar 

  • Roush, W.R., Hoong, L.K., Palmer, M.A.J., Straub, J.A., Palkowitz, A.D., 1990b. Asymmetric synthesis using tartrate ester modified allylboronates. 2. Single and double asymmetric reactions with alkoxy-substituted aldehydes.J. Org. Chem.,55:4117–4126.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Center of Unilab Chemical Engineering Reaction & Department of Chemical Engineering, Zhejiang University, 310027, Hangzhou, China

    Chen Wan-suo & Zhi-rong Chen

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  1. Chen Wan-suo
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  2. Zhi-rong Chen
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Correspondence to Chen Wan-suo.

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Chen, Ws., Chen, Zr. Quantum chemical study on asymmetric allylation of benzaldehyde in the presence of chiral allylboronate. J Zheijang Univ Sci B 6, 606–610 (2005). https://doi.org/10.1631/jzus.2005.B0606

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  • DOI: https://doi.org/10.1631/jzus.2005.B0606

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