Bürgi–Dunitz angle

The Bürgi–Dunitz angle (BD angle) is one of two angles that fully define the geometry of "attack" (approach via collision) of a nucleophile on a trigonal unsaturated center in a molecule, originally the carbonyl center in an organic ketone, but now extending to aldehyde, ester, and amide carbonyls, and to alkenes (olefins) as well.[1][2][3] The angle was named after crystallographers Hans-Beat Bürgi and Jack D. Dunitz, its first senior investigators.

Practically speaking, the Bürgi–Dunitz and Flippin–Lodge angles were central to the development of understanding of chiral chemical synthesis, and specifically of the phenomenon of asymmetric induction during nucleophilic attack at hindered carbonyl centers (see the Cram–Felkin–Anh and Nguyen models).[4][5]

Additionally, the stereoelectronic principles that underlie nucleophiles adopting a proscribed range of Bürgi–Dunitz angles may contribute to the conformational stability of proteins[6][7] and are invoked to explain the stability of particular conformations of molecules in one hypothesis of a chemical origin of life.[8]

  1. ^ Fleming, I. (2010) Molecular Orbitals and Organic Chemical Reactions: Reference Edition, John Wiley & Sons, pp. 214–215.
  2. ^ Bürgi, H.-B.; Dunitz, J. D.; Lehn. J.-M.; Wipff, G. (1974). "Stereochemistry of reaction paths at carbonyl centres". Tetrahedron. 30 (12): 1563–1572. doi:10.1016/S0040-4020(01)90678-7.
  3. ^ Cieplak, A.S. (2008) Organic addition and elimination reactions: Transformation paths of carbonyl derivatives In Structure Correlation, Vol. 1 (H.-B. Bürgi & J. D. Dunitz, eds.), New York:John Wiley & Sons, pp. 205–302, esp. 216-218. [doi:10.1002/9783527616091.ch06; ISBN 9783527616091 ]
  4. ^ Cite error: The named reference Heathcock1990 was invoked but never defined (see the help page).
  5. ^ Gawley, R.E. & Aube, J. 1996, Principles of Asymmetric Synthesis (Tetrahedron Organic Chemistry Series, Vo. 14), pp. 121-130, esp. pp. 127f.
  6. ^ Bartlett, G.J.; Choudhary, A.; Raines, R.T.; Woolfson, D.N. (2010). "n→π* interactions in proteins". Nat. Chem. Biol. 6 (8): 615–620. doi:10.1038/nchembio.406. PMC 2921280. PMID 20622857.
  7. ^ Fufezan, C. (2010). "The role of Buergi-Dunitz interactions in the structural stability of proteins". Proteins. 78 (13): 2831–2838. doi:10.1002/prot.22800. PMID 20635415. S2CID 41838636.
  8. ^ Choudhary, A.; Kamer, K.J.; Powner, M.W.; Sutherland, J.D.; Raines, R.T. (2010). "A stereoelectronic effect in prebiotic nucleotide synthesis". ACS Chem. Biol. 5 (7): 655–657. doi:10.1021/cb100093g. PMC 2912435. PMID 20499895.
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