{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,13]],"date-time":"2026-06-13T02:10:40Z","timestamp":1781316640294,"version":"3.54.1"},"reference-count":30,"publisher":"American Chemical Society (ACS)","issue":"22","content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J. Org. Chem."],"published-print":{"date-parts":[[2008,11,21]]},"DOI":"10.1021\/jo801996b","type":"journal-article","created":{"date-parts":[[2008,10,24]],"date-time":"2008-10-24T06:04:11Z","timestamp":1224828251000},"page":"9102-9108","source":"Crossref","is-referenced-by-count":39,"title":["Nonplanar Structures of Thioamides Derived from 7-Azabicyclo[2.2.1]heptane. Electronically Tunable Planarity of Thioamides"],"prefix":"10.1021","volume":"73","author":[{"given":"Tetsuharu","family":"Hori","sequence":"first","affiliation":[{"name":"Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan, and Department of Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, 1314-1 Shido, Sanuki, Kagawa 769-2193, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuko","family":"Otani","sequence":"additional","affiliation":[{"name":"Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan, and Department of Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, 1314-1 Shido, Sanuki, Kagawa 769-2193, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Masatoshi","family":"Kawahata","sequence":"additional","affiliation":[{"name":"Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan, and Department of Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, 1314-1 Shido, Sanuki, Kagawa 769-2193, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Kentaro","family":"Yamaguchi","sequence":"additional","affiliation":[{"name":"Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan, and Department of Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, 1314-1 Shido, Sanuki, Kagawa 769-2193, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tomohiko","family":"Ohwada","sequence":"additional","affiliation":[{"name":"Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan, and Department of Pharmaceutical Sciences at Kagawa Campus, Tokushima Bunri University, 1314-1 Shido, Sanuki, Kagawa 769-2193, Japan"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2008,10,24]]},"reference":[{"key":"ref1\/cit1","doi-asserted-by":"crossref","first-page":"2318","DOI":"10.1021\/j100866a055","volume":"71","author":"Sandstr\u00f6m J.","year":"1967","journal-title":"J. Phys. Chem."},{"key":"ref2\/cit2","doi-asserted-by":"crossref","first-page":"3532","DOI":"10.1021\/j100692a008","volume":"75","author":"Neuman R. C.","year":"1971","journal-title":"J. Phys. Chem."},{"key":"ref3\/cit3a","doi-asserted-by":"crossref","first-page":"2201","DOI":"10.1021\/ja00113a009","volume":"117","author":"Wiberg K. B.","year":"1995","journal-title":"J. Am. Chem. Soc."},{"key":"ref3\/cit3b","doi-asserted-by":"crossref","first-page":"9478","DOI":"10.1021\/ja9639426","volume":"119","author":"Lauvergnat D.","year":"1997","journal-title":"J. Am. Chem. Soc."},{"key":"ref4\/cit4","unstructured":"For a counter-example to the resonance effect, see:"},{"key":"ref4\/cit4a","doi-asserted-by":"crossref","first-page":"1737","DOI":"10.1021\/ja952678y","volume":"118","author":"Laidig K. E.","year":"1996","journal-title":"J. Am. Chem. Soc."},{"key":"ref5\/cit5","doi-asserted-by":"crossref","first-page":"5854","DOI":"10.1021\/jp034919r","volume":"107","author":"Galabov B.","year":"2003","journal-title":"J. Phys. Chem. A"},{"key":"ref6\/cit6","doi-asserted-by":"crossref","first-page":"4655","DOI":"10.1021\/ol027056d","volume":"4","author":"Miwa J. H.","year":"2002","journal-title":"Org. Lett."},{"key":"ref7\/cit7","doi-asserted-by":"crossref","first-page":"433","DOI":"10.1021\/ja00157a064","volume":"112","author":"Sherman D. B.","year":"1990","journal-title":"J. Am. Chem. Soc."},{"key":"ref8\/cit8","doi-asserted-by":"crossref","first-page":"12200","DOI":"10.1021\/ja982398t","volume":"120","author":"Artis D. R.","year":"1998","journal-title":"J. Am. Chem. Soc."},{"key":"ref9\/cit9","doi-asserted-by":"crossref","first-page":"8079","DOI":"10.1021\/ja8015044","volume":"130","author":"Reiner A.","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"ref10\/cit10","doi-asserted-by":"crossref","first-page":"865","DOI":"10.1016\/S0040-4039(97)10751-1","volume":"39","author":"Ohwada T.","year":"1998","journal-title":"Tetrahedron Lett."},{"key":"ref11\/cit11","doi-asserted-by":"crossref","first-page":"15191","DOI":"10.1021\/ja036644z","volume":"125","author":"Otani Y.","year":"2003","journal-title":"J. Am. Chem. Soc."},{"key":"ref12\/cit12","doi-asserted-by":"crossref","first-page":"169","DOI":"10.1016\/0022-2836(71)90419-0","volume":"59","author":"Winkler F. K.","year":"1971","journal-title":"J. Mol. Biol."},{"key":"ref13\/cit13","unstructured":"This is due to high-density packing of1fwith aZ-value of 8 and an aromatic stacking distance of 3.4 \u00c5."},{"key":"ref14\/cit14","doi-asserted-by":"crossref","first-page":"517","DOI":"10.1021\/cr60267a001","volume":"70","author":"Stewart W. E.","year":"1970","journal-title":"Chem. Rev."},{"key":"ref15\/cit15","volume-title":"Applications of Dynamic NMR Spectroscopy to Organic Chemistry","volume":"4","author":"Oki M.","year":"1985"},{"key":"ref16\/cit16","first-page":"319","volume":"46","author":"Ammann C.","year":"1982","journal-title":"J. Magn. Reson."},{"key":"ref17\/cit17","doi-asserted-by":"crossref","first-page":"165","DOI":"10.1021\/cr00002a004","volume":"91","author":"Hansch C.","year":"1991","journal-title":"Chem. Rev."},{"key":"ref18\/cit18","unstructured":"Regression coefficients (r) and regression slopes (\u03c1+) of corresponding amides are as follows (see ref11):r= 0.98, \u03c1+= 0.61 for4andr= 0.99 and \u03c1+= 0.82 for5."},{"key":"ref19\/cit19","doi-asserted-by":"crossref","first-page":"10125","DOI":"10.1021\/ja028751j","volume":"125","author":"Olsen R. A.","year":"2003","journal-title":"J. Am. Chem. Soc."},{"key":"ref20\/cit20","unstructured":"The fact that the negative entropic contribution is larger in more polar nitrobenzene than ino-dichlorobenzene can be partially explained in terms of enhanced solvation of thioamides, especially of the bicyclic thioamides, upon rotation. As for solvent effects on thioamide rotation, see:"},{"key":"ref20\/cit20a","doi-asserted-by":"crossref","first-page":"2038","DOI":"10.1021\/ja003586y","volume":"123","author":"Wiberg K. B.","year":"2001","journal-title":"J. Am. Chem. Soc."},{"key":"ref21\/cit21a","doi-asserted-by":"crossref","first-page":"323","DOI":"10.1002\/mrc.1260240411","volume":"24","author":"Pinto B. M.","year":"1986","journal-title":"Magn. Reson. Chem."},{"key":"ref21\/cit21b","doi-asserted-by":"crossref","first-page":"3024","DOI":"10.1021\/jp027696y","volume":"107","author":"Suarez C.","year":"2003","journal-title":"J. Phys. Chem. A"},{"key":"ref22\/cit22","unstructured":"\u0394His equal to the difference of potential energyEplusRT, zero-point energy, and the thermal corrections. Thus, it is well accepted that \u0394H\u29e7is approximately equal to \u0394E(which is obtained by calculation) along the reaction coordinate. See:"},{"key":"ref22\/cit22a","doi-asserted-by":"crossref","first-page":"682","DOI":"10.1002\/anie.199206821","volume":"31","author":"Houk K. N.","year":"1992","journal-title":"Angew. Chem., Int. Ed. Engl."},{"key":"ref23\/cit23","unstructured":"The planarity (in terms of \u03b1 value) of the calculated structures of the thioamides was also dependent on the electron-withdrawing nature of the aromatic substituents. In the case of the bicyclic thioamides1:1h(R = NO2) 160.7\u00b0 >1g(R = CN) 160.1\u00b0 >1f(R = COOMe) 159.8\u00b0 >1e(R = Cl) 158.8\u00b0 >1a(R = H) \u22481d(R = CH3) 158.1\u00b0 >1c(R = OMe) 157.2\u00b0 >1b(R = N(CH3)2) 156.0\u00b0. In the case of the monocyclic2:2h(R = NO2) 172.5\u00b0 >2g(R = CN) \u22482f(R = COOMe) 172.0\u00b0 >2e(R = Cl) 171.3\u00b0 \u22482a(R = H) 171.5\u00b0 \u22482d(R = CH3) 171.2\u00b0 >2c(R = OMe) 170.3\u00b0 >2b(R = N(CH3)2) 169.5\u00b0. The dependency of2was smaller than that of1, which was consistent with the trend found in the crystal structures. See Table S1 inSupporting Information."},{"key":"ref24\/cit24","unstructured":"We thank an anonymous reviewer for valuable comment about the contribution of resonance structure D."},{"key":"ref25\/cit25","doi-asserted-by":"crossref","first-page":"112","DOI":"10.1107\/S0108767307043930","volume":"64","author":"Sheldrick G. M.","year":"2008","journal-title":"Acta Crystallogr."}],"container-title":["The Journal of Organic Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jo801996b","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,3,9]],"date-time":"2023-03-09T14:17:39Z","timestamp":1678371459000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/doi\/10.1021\/jo801996b"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2008,10,24]]},"references-count":30,"journal-issue":{"issue":"22","published-print":{"date-parts":[[2008,11,21]]}},"alternative-id":["10.1021\/jo801996b"],"URL":"https:\/\/doi.org\/10.1021\/jo801996b","relation":{},"ISSN":["0022-3263","1520-6904"],"issn-type":[{"value":"0022-3263","type":"print"},{"value":"1520-6904","type":"electronic"}],"subject":[],"published":{"date-parts":[[2008,10,24]]}}}