Baldwin's Rules - Department of Medicinal Chemistry

Chemical Reviews REVIEW
radical cyclizations, cascade transformations of alkynes for the
construction of graphene nanoribbons, electronic and conformational
control of the Bergman cyclization, conformationally gated
cyclization/fragmentation pathways which provide a potential biochemical
autoprotection mechanism from DNA-damaging cycloaromatization,
metal-free conversion of phenols into esters
and amides of aromatic carboxylic acids, as well as studies of stereoelectronic
and rehybridization effects in organic and supramolecular
chemistry.
ACKNOWLEDGMENT
I.V.A. is funded in part by the National Science Foundation
(CHE-0848686) and Petroleum Research Fund, administered
by the American Chemical Society (Award 47590-AC4). A
planning grant from FSU-COFRC is also gratefully appreciated.
REFERENCES
(1) Dictionary of Natural Products, version 14.1; Chapman & Hall/
CRC Informa: London, 2005.
(2) (a) Koch, M. A.; Schuffenhauer, A.; Scheck, M.; Wetzel, S.;
Casaulta, M.; Odermatt, A.; Ertl, P.; Waldmann, H. Proc. Natl. Acad. Sci.
U.S.A. 2005, 102, 17272. (b) Bon, R. S.; Waldmann, H. Acc. Chem. Res.
2010, 43, 1103.
(3) http://www.rsc.org/publishing/journals/cc/news/top40mostcitedarticles.asp.
(4) Baldwin, J. E. J. Chem. Soc., Chem. Commun. 1976, 734.
(5) Johnson, C. D. Acc. Chem. Res. 1993, 26, 476.
(6) Baldwin, J. E.; Kruse, L. I. J. Chem. Soc., Chem. Commun.
1977, 233.
(7) Baldwin, J. E.; Lusch, M. J. Tetrahedron 1982, 38, 2939.
(8) Crich, D.; Fortt, S. M. Tetrahedron Lett. 1987, 28, 2895.
(9) Rules regarding the closure of enolates were published subsequently
and included the additional constraint requiring the alignment
of the enolate π-orbitals with those of the breaking bond. The rules were
limited to exo-tet and exo-trig closures. 3-, 4-, and 5-(Enolendo)closures
(for both exo-tet and exo-trig modes) were suggested to be
disfavored, while 5- and 6-(enolendo)- and 3- to 7-(enolexo)- were said
to be favored, see refs 5 and 6.
(10) (a) Curran, D. P.; Shen, W. J. Am. Chem. Soc. 1993, 115, 6051.
(b) Curran, D. P.; Kim, D.; Liu, H. T.; Shen, W. J. Am. Chem. Soc. 1988,
110, 5900. (c) Robertson, J.; Pillai, J.; Lush, R. K. Chem.Soc.Rev.2001, 30, 94.
(11) Beckwith, A. L. J.; Easton, C. J.; Serelis, A. K. J. Chem. Soc.,
Chem. Commun. 1980, 482. For an earlier work, see also: Julia, M. Pure
Appl. Chem. 1967, 15, 167. Beckwith, A. L. J. Chem. Soc. Special Publ. No.
24 1970, 239.
(12) Note that this guideline disagrees with the Baldwin rules
predicting 3-exo- and 4-exo-dig cyclizations to be unfavorable.
(13) (a) Beckwith, A. L. J.; Schiesser, C. H. Tetrahedron 1985,
41, 3925. (b) Spellmeyer, D. C.; Houk, K. N. J. Org. Chem. 1987,
52, 959. (c) Tripp, J. C.; Schiesser, C. H.; Curran, D. P. J. Am. Chem. Soc.
2005, 127, 5518.
(14) (a) Parsons, A. F. C. R. Acad. Sci. Paris, Ser. IIc: Chem. 2001,
4, 391. (b) H. Ishibashi, H.; Sato, T.; Ikeda, M. Synthesis 2002, 6, 695.
(c) Chatgilialoglu, C.; Ferreri, C.; Guerra, M.; Timokhin, V.; Froudakis,
G.; Gimisis, T. J. Am. Chem. Soc. 2002, 124, 10765.
(15) Gilmore, K.; Alabugin, I. Handb. Radical Chem. 2011.
(16) B€urgi, H. B.; Dunitz, J. D.; Lehn, J. M.; Wipff, G.Tetrahedron
1974, 30, 1563.
(17) Guthrie, J. P.; Guo, J. J. Am. Chem. Soc. 1996, 118, 11472.
(18) Wegner, G. Polym. Lett. 1971, 9, 133.
(19) Baughman, R. H. J. Appl. Phys. 1972, 43, 4362.
(20) (a) Dessy, R. E.; Kandil, S. A. J. Org. Chem. 1965, 30, 3857.
(b) Kandil, S. A.; Dessy, R. E. J. Am. Chem. Soc. 1966, 88, 3027.
(21) (a) Strozier, R. W.; Caramella, P.; Houk, K. N. J. Am. Chem. Soc.
1979, 101, 1340. See also: (b) Houk, K. N.; Strozier, R. W.; Rozeboom,
M. D.; Nagaze, S. J. Am. Chem. Soc. 1982, 104, 323.
(22) Houk, K. N.; Rondan, N. G.; Schleyer, P. v. R.; Kaufmann, E.;
Clark, T. J. Am. Chem. Soc. 1985, 107, 2821.
(23) (a) Elliott, R. J.; Richards, W. G. THEOCHEM 1982, 87, 247.
(b) Perkins, M. J.; Wong, P. C.; Barrett, J.; Shalival, G. J. Org. Chem.
1981, 46, 2196. (c) Ersenstein, O.; Procter, G.; Dunitz, J. D. Helv. Chim.
Acta 1978, 61, 1538. (d) Dykstra, C. E.; Arduengo, A. J.; Fukunaga, F. T.
J. Am. Chem. Soc. 1978, 100, 6007. (e) Klimenko, N. M.; Bozhenko,
K. V.; Strunina, E. V.; Rykova, E. A.; Temkin, O. N. THEOCHEM 1999,
490, 233.
(24) Alabugin, I. V.; Gilmore, K.; Manoharan, M. J. Am. Chem. Soc.
2011, DOI: 10.1021/ja203191f.
(25) The intrinsic barriers were estimated via removal of thermonamic
contribution to the activation barrier using Marcus theory (vide infra).
(26) (a) Tomooka, K.; Yamamoto, H.; Nakai, T. J. Am. Chem. Soc.
1996, 118, 3317. (b) Tomooka, K.; Yamamoto, H.; Nakai, T. Liebigs
Ann./Rec. 1997, 1275.
(27) Paddon-Row, M. N.; Rondan, N. G.; Houk, K. N. J. Am. Chem.
Soc. 1982, 104, 7162.
(28) Electrophilic closures should not be confused with the much
more common electrophile-promoted nucleophilic closures (EPNC)
discussed in this section. EPNC are often misleadingly referred as
electrophilic cyclizations.
(29) (a) Slegt, M.; Gronheid, R.; Vlugt, D. v. d.; Ochiai, M.;
Okuyama, T.; Zuilhof, H.; Overkleeft, H. S.; Lodder, G. J. Org. Chem.
2006, 71, 2227. (b) Miyamoto, K.; Shiro, M.; Ochai, M. Angew. Chem.,
Int. Ed. 2009, 48, 8931.
(30) Mayr, H.; Schneider, R.; Wilhelm, D.; Schleyer, P. v. R. J. Org.
Chem. 1981, 46, 5336.
(31) (a) Koch, W.; Liu, B.; DeFrees, D. J. J. Am. Chem. Soc. 1988,
110, 7325. (b) Saunders, M.; Laidig, K. E.; Wiberg, K. B.; Schleyer,
P. v. R. J. Am. Chem. Soc. 1988, 110, 7652.
(32) Overman, L. E.; Sharp, M. J. J. Am. Chem. Soc. 1988, 110,
612–614.
(33) Overman, L. E.; Sharp, M. J. J. Am. Chem. Soc. 1988, 110, 5934.
(34) Godoi, B.; Schumacher, R. F.; Zeni, G. Chem. Rev. 2011, 111, 2937.
(35) Carpenter, B. K. Annu. Rev. Phys. Chem. 2005, 56, 57.
(36) Ess, D. H.; Houk, K. N. J. Am. Chem. Soc. 2007, 129, 10646.
(37) Borden, W. T. Chem. Rev. 1989, 89, 1095.
(38) Jemmis, E. D.; Buss, V.; Schleyer, P. V. R.; Allen, L. C. J. Am.
Chem. Soc. 1976, 98, 6483.
(39) Alabugin, I. V.; Manoharan, M.; Buck, M.; Clark, R. J. THEO-
CHEM 2007, 813, 21.
(40) Volland, W. V.; Davidson, E. R.; Borden, W. T. J. Am. Chem. Soc.
1979, 101, 533.
(41) Houk, K. N. In Stereochemistry and Reactivity of Systems Containing
π Electrons; Verlag Chemie International: Deerfield Beach, FL,
1983; p 1.
(42) Hrovat, D. A.; Borden, W. T. J. Am. Chem. Soc. 1988, 110, 4710.
(43) Ess, D. H.; Jones, G. O.; Houk, K. N. Org. Lett. 2008, 10, 1633.
(44) (a) Agard, N. J.; Prescher, J. A.; Bertozzi, C. R. J. Am. Chem. Soc.
2004, 126, 15046. (b) Lutz, J. -F. Angew. Chem., Int. Ed. 2008, 47, 2182.
(c) Ning, X.; Guo, J.; Wolfert, M. A.; Boons, G.-J. Angew. Chem., Int. Ed.
2008, 47, 2253. (d) Agard, N. J.; Baskin, J. M; Prescher, J. A.; Lo, A.;
Bertozzi, C. R. ACS Chem. Biol. 2006, 1, 644. (e) Nguyen, L. T.; De Proft,
F.; Dao, V. L.; Ngyuen, M. T.; Geerlings, P. J. Phys. Org. Chem. 2003,
16, 615.
(45) Maier, W. F.; Lau, G. C.; McEwen, A. B. J. Am. Chem. Soc. 1985,
107, 4724.
(46) For the effect on alkyne bending in the Bergman cyclization:
(a) Alabugin, I. V.; Manoharan, M. J. Phys. Chem. A 2003, 107, 3363.
(b) Galbraith, J. M.; Schreiner, P. R.; Harris, N.; Wei, W.; Wittkopp, A.;
Shaik, S. Chem.—Eur. J. 2000, 6, 1446.
(47) Most of the reactant destabilization that contributes to the
increased reactivity of cyclic enediynes stems from the Pauli repulsion of
filled in-plane p-orbitals and symmetry cancellation of the two-electron
AM dx.doi.org/10.1021/cr200164y |Chem. Rev. XXXX, XXX, 000–000