{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,29]],"date-time":"2026-04-29T20:32:27Z","timestamp":1777494747840,"version":"3.51.4"},"reference-count":38,"publisher":"American Chemical Society (ACS)","issue":"22","content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J. Org. Chem."],"published-print":{"date-parts":[[2004,10,1]]},"DOI":"10.1021\/jo048980j","type":"journal-article","created":{"date-parts":[[2004,10,22]],"date-time":"2004-10-22T04:49:09Z","timestamp":1098420549000},"page":"7479-7485","source":"Crossref","is-referenced-by-count":13,"title":["New Paradigms for the Peroxy Acid Epoxidation of CC Double Bonds:\u2009 The Role of the Peroxy Acid s-Trans Conformer and of the 1,2-H Transfer in the Epoxidation of Cyclic Allylic Alcohols"],"prefix":"10.1021","volume":"69","author":[{"given":"Mauro","family":"Freccero","sequence":"first","affiliation":[{"name":"Dipartimento di Chimica Organica, Universit\u00e0 di Pavia, Viale Taramelli 10, 27100 Pavia, Italy, and Dipartimento di Chimica, Universit\u00e0 di Modena, Via Campi 183, 41100 Modena, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Remo","family":"Gandolfi","sequence":"additional","affiliation":[{"name":"Dipartimento di Chimica Organica, Universit\u00e0 di Pavia, Viale Taramelli 10, 27100 Pavia, Italy, and Dipartimento di Chimica, Universit\u00e0 di Modena, Via Campi 183, 41100 Modena, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Mirko","family":"Sarzi-Amad\u00e8","sequence":"additional","affiliation":[{"name":"Dipartimento di Chimica Organica, Universit\u00e0 di Pavia, Viale Taramelli 10, 27100 Pavia, Italy, and Dipartimento di Chimica, Universit\u00e0 di Modena, Via Campi 183, 41100 Modena, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Augusto","family":"Rastelli","sequence":"additional","affiliation":[{"name":"Dipartimento di Chimica Organica, Universit\u00e0 di Pavia, Viale Taramelli 10, 27100 Pavia, Italy, and Dipartimento di Chimica, Universit\u00e0 di Modena, Via Campi 183, 41100 Modena, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"316","published-online":{"date-parts":[[2004,9,25]]},"reference":[{"key":"jo048980jb00001\/jo048980jb00001_1","doi-asserted-by":"crossref","first-page":"5155","DOI":"10.1021\/jo010285d","volume":"66","author":"Erzen E.","year":"2001","journal-title":"J. Org. Chem."},{"key":"jo048980jb00001\/jo048980jb00001_2","unstructured":"(b) According to these authors, the calculated potential energy difference between s-trans (\u03bc = 3.11 D) and s-cis (\u03bc = 1.43 D) performic is of 2.01 kcal\/mol at the B3LYP\/6-311++G(d,p) level in gas phase. Our B3LYP\/6-311++G(3df,2pd) calculations led to the following results:\u2009 \u03bcs-cis= 1.36 D (gas), 1.45 D (benzene), 1.51 D (CH2Cl2) and \u03bcs-trans= 3.09 D (gas), 3.38 D (benzene), 3.67 D (CH2Cl2); (Gs-trans\u2212Gs-cis)gas= 2.48 kcal\/mol, (Gs-trans\u2212Gs-cis)benzene= 1.77 kcal\/mol, (Gs-trans\u2212Gs-cis)CH2Cl2= 0.62 kcal\/mol."},{"key":"jo048980jb00001\/jo048980jb00001_3","doi-asserted-by":"crossref","first-page":"740","DOI":"10.1021\/jo00828a044","volume":"35","author":"Curci R.","year":"1970","journal-title":"J. Org. Chem."},{"key":"jo048980jb00002\/jo048980jb00002_1","unstructured":"The s-cis form of neutral peroxy acids has always been assumed as the only reactive conformer in all theoretical studies on epoxidation reactions of both alkenes and allylic alcohols.3-5"},{"key":"jo048980jb00003\/jo048980jb00003_1","doi-asserted-by":"crossref","first-page":"680","DOI":"10.1021\/ja9717976","volume":"120","author":"Bach R. D.","year":"1998","journal-title":"J. Am. Chem. Soc."},{"key":"jo048980jb00003\/jo048980jb00003_2","doi-asserted-by":"crossref","first-page":"9902","DOI":"10.1021\/ja980495g","volume":"120","author":"Bach R. D.","year":"1998","journal-title":"J. Am. Chem. Soc."},{"key":"jo048980jb00003\/jo048980jb00003_3","doi-asserted-by":"crossref","first-page":"6715","DOI":"10.1021\/jo0009548","volume":"65","author":"Adam W.","year":"2000","journal-title":"J. Org. Chem."},{"key":"jo048980jb00003\/jo048980jb00003_4","doi-asserted-by":"crossref","first-page":"924","DOI":"10.1021\/ja026882e","volume":"125","author":"Bach R. D.","year":"2003","journal-title":"J. Am. Chem Soc."},{"key":"jo048980jb00003\/jo048980jb00003_5","doi-asserted-by":"crossref","first-page":"4300","DOI":"10.1021\/jp034391q","volume":"107","author":"Bach R. D.","year":"2003","journal-title":"J. Phys. Chem. A"},{"key":"jo048980jb00004\/jo048980jb00004_1","doi-asserted-by":"crossref","first-page":"10147","DOI":"10.1021\/ja963847x","volume":"119","author":"Houk K. N.","year":"1997","journal-title":"J. Am. Chem. Soc."},{"key":"jo048980jb00004\/jo048980jb00004_2","doi-asserted-by":"crossref","first-page":"4485","DOI":"10.1002\/1521-3773(20011203)40:23<4485::AID-ANIE4485>3.0.CO;2-N","volume":"40","author":"Houk K. N.","year":"2001","journal-title":"Angew. Chem., Int. Ed."},{"key":"jo048980jb00004\/jo048980jb00004_3","doi-asserted-by":"crossref","first-page":"2661","DOI":"10.1021\/ol026105j","volume":"4","author":"Washington I.","year":"2002","journal-title":"Org. Lett."},{"key":"jo048980jb00005\/jo048980jb00005_1","doi-asserted-by":"crossref","first-page":"11309","DOI":"10.1016\/S0040-4020(99)00630-4","volume":"55","author":"Freccero M.","year":"1999","journal-title":"Tetrahedron."},{"key":"jo048980jb00005\/jo048980jb00005_2","doi-asserted-by":"crossref","first-page":"3853","DOI":"10.1021\/jo981743u","volume":"64","author":"Freccero M.","year":"1999","journal-title":"J. Org. Chem."},{"key":"jo048980jb00005\/jo048980jb00005_3","doi-asserted-by":"crossref","first-page":"2030","DOI":"10.1021\/jo991530k","volume":"65","author":"Freccero M.","year":"2000","journal-title":"J. Org. Chem."},{"key":"jo048980jb00005\/jo048980jb00005_4","doi-asserted-by":"crossref","first-page":"8948","DOI":"10.1021\/jo000900y","volume":"65","author":"Freccero M.","year":"2000","journal-title":"J. Org. Chem."},{"key":"jo048980jb00005\/jo048980jb00005_5","doi-asserted-by":"crossref","first-page":"8519","DOI":"10.1021\/jo026141w","volume":"67","author":"Freccero M.","year":"2002","journal-title":"J. Org. Chem."},{"key":"jo048980jb00006\/jo048980jb00006_1","first-page":"47","volume":"11","author":"Bartlett P. D.","year":"1950","journal-title":"Rec. Chem. Prog."},{"key":"jo048980jb00007\/jo048980jb00007_1","volume-title":"\u201cBartlett mechanism","author":"Plesnicar"},{"key":"jo048980jb00008\/jo048980jb00008_1","doi-asserted-by":"crossref","first-page":"5191","DOI":"10.1021\/jo950930e","volume":"62","author":"Ss","year":"1997","journal-title":"J. Org. Chem."},{"key":"jo048980jb00009\/jo048980jb00009_2","doi-asserted-by":"crossref","first-page":"2903","DOI":"10.1021\/jo034087t","volume":"68","author":"de Visser S. P.","year":"2003","journal-title":"J. Org. Chem."},{"key":"jo048980jb00009\/jo048980jb00009_3","volume":"90","author":"On","year":"1968","journal-title":"J. Am. Chem. Soc."},{"key":"jo048980jb00010\/jo048980jb00010_1","doi-asserted-by":"crossref","first-page":"6123","DOI":"10.1016\/S0040-4020(98)00305-6","volume":"54","author":"Freccero M.","year":"1998","journal-title":"Tetrahedron"},{"key":"jo048980jb00011\/jo048980jb00011_1","volume-title":"respectively, conformer of performic acid","author":"The"},{"key":"jo048980jb00012\/jo048980jb00012_1","unstructured":"(a) B3LYP\/6-311+G(d,p) calculations showed thatcis,syn,endo-3ais less stable (free energy at 298.15 K) thancis,syn,exo-2aby 2.85 kcal\/mol (gas phase), 3.39 kcal\/mol (benzene solution), and 3.42 kcal\/mol (CH2Cl2solution). Likewisecis,syn,endo-3bis less stable (free energy at 298.15 K) thancis,syn,exo-2bby 2.40 kcal\/mol (gas phase), 2.87 kcal\/mol (benzene solution), and 2.97 kcal\/mol (CH2Cl2solution). See also ref 5d for 2-cyclohexenol data."},{"key":"jo048980jb00012\/jo048980jb00012_2","unstructured":"(b) The free energy (at 298.15 K) of TStrans,syn,endo-4a(n= 1) is lower by 7.40 kcal\/mol (gas phase) and 6.43 kcal\/mol (benzene solution) than that of TStrans,syn,exo-5a(n= 1) at the B3LYP\/6-311+G(d,p) level.The latter transition structure is not a stationary point in dichloromethane solution (i.e., all our attempts to locate it led either to starting reactants or to products). Moreover, at the same theory level TStrans,syn,endo-4b(n= 2) resides at lower free energy than TStrans,syn,exo-5bby 8.2 kcal\/mol in gas phase but when optimization was performed at the B3LYP\/level the latter TS collapsed to the corresonding cis,syn,endo TS in which the peroxy acid acts as hydrogen bond donor."},{"key":"jo048980jb00012\/jo048980jb00012_3","unstructured":"(c) As for wave functions of TSs deriving from s-trans performic acid, TSs of type4were always found stable (not only in the case of the reactions of cyclic allylic alcohols but also in the case of those of acyclic allylic alcohols) while wave functions of TSs of type5or7may show a slight instability. For example, the wave function of TStrans,syn,exo-5aexhibits a small RHF\u00b7\u00b7\u00b7UHF instability [0.25 kcal\/mol, \u3008S2\u3009 = 0.163 with the B3LYP\/6-311+G(d,p) method], TStrans,anti,exo-7b(n= 2) is stable while TStrans,anti,exo-7a(n= 1) has a very small instability [0.04 kcal\/mol, \u3008S2\u3009 = 0.066 with the B3LYP\/6-311+G(d,p) method]."},{"key":"jo048980jb00013\/jo048980jb00013_1","volume-title":"Gaussian 03, revision B.02","author":"Frisch M. J.","year":"2003"},{"key":"jo048980jb00014\/jo048980jb00014_1","doi-asserted-by":"crossref","first-page":"9395","DOI":"10.1021\/ja030245m","volume":"125","author":"Wu A.","year":"2003","journal-title":"J. Am. Chem. Soc."},{"key":"jo048980jb00014\/jo048980jb00014_2","doi-asserted-by":"crossref","first-page":"2305","DOI":"10.1021\/jp035869t","volume":"108","author":"Xu X.","year":"2004","journal-title":"J. Phys. Chem. A"},{"key":"jo048980jb00016\/jo048980jb00016_1","doi-asserted-by":"crossref","first-page":"4215","DOI":"10.1016\/S0040-4039(02)00747-5","volume":"43","author":"Okovytyy S.","year":"2002","journal-title":"Tetrahedron Lett."},{"key":"jo048980jb00017\/jo048980jb00017_1","doi-asserted-by":"crossref","first-page":"4965","DOI":"10.1021\/ja00122a028","volume":"117","author":"Rastelli A.","year":"1995","journal-title":"J. Am. Chem. Soc."},{"key":"jo048980jb00018\/jo048980jb00018_1","volume-title":"perpendicular","author":"The"},{"key":"jo048980jb00019\/jo048980jb00019_1","unstructured":"Electron transfer from allylic alcohols to performic acid, at the TS, is of the same order of magnitude (\u22120.3\u22120.4 e) for both TSs2and TSs4{TS2a[B3LYP\/6-311+G(d,p)]: \u22120.40e (NPA) and \u22120.30e (CHELPG) in the gas phase,0.39e (NPA) and \u22120.32e (CHELPG) in dichloromethane; TS4a[B3LYP\/6-311+G(d,p)]: \u22120.42e (NPA) and \u22120.36e (CHELPG) in the gas phase, \u22120.37e (NPA) and \u22120.33e (CHELPG) in dichloromethane}. The net charge at C6H is always more positive than that at C7H of the cyclobutenol moiety in both TSs2and TSs4{B3LYP\/6-311+G(d,p) calculations (gas phase), TS2a:\u2009 +0.177e (NPA) and +0.160e (CHELPG) at C6H, +0.143 (NPA) and \u22120.115e (CHELPG) at C7H.; TS4a:\u2009 +0.185e (NPA) and +0.185e (CHELPG) at C6H, +0.125 (NPA) and \u22120.137e (CHELPG) at C7H. B3LYP\/6-311+G(d,p) calculations (dichloromethane), TS2a:\u2009 +0.192e (NPA) and +0.223e (CHELPG) at C6H, +0.108 (NPA) and \u22120.152e (CHELPG) at C7H; TS4a:\u2009 +0.174e (NPA) and +0.200e (CHELPG) at C6H, +0.121 (NPA) and \u22120.142e (CHELPG) at C7H. The net charge on the H1O2group is close to 0, slightly positive and negative, respectively, according to NPA and CHELPG methods in both TSs2and TSs4{B3LYP\/6-311+G(d,p) calculations, TS2a: \u22120.06e (NPA) and +0.09e (CHELPG) in the gas phase and \u22120.05e (NPA) and +0.08e (CHELPG) in dichloromethane; TS4a: \u22120.06e (NPA) and +0.08e (CHELPG) in the gas phase and \u22120.03e (NPA) and +0.09e (CHELPG) in dichloromethane."},{"key":"jo048980jb00020\/jo048980jb00020_1","doi-asserted-by":"crossref","first-page":"255","DOI":"10.1002\/anie.199402551","volume":"33","author":"Herges R.","year":"1994","journal-title":"Angew. Chem., Int. Ed. Engl."},{"key":"jo048980jb00021\/jo048980jb00021_1","unstructured":"The presence of the first-order saddle point4a,on the potential energy surface of the reaction of performic acid with cyclobutenol, was confirmed by calculations with quite large basis sets [e.g., B3LYP\/6-311++(3df,2pd) (E4a\u2212E2a= 0.76 kcal\/mol, gas phase) and B3LYP\/ccp-VTZ (B3LYP\/aug-ccp-VTZ\/\/B3LYP\/ccp-VTZ,E4a\u2212E2a= 0.84 kcal\/mol, gas phase)."},{"key":"jo048980jb00022\/jo048980jb00022_1","unstructured":"For example, TS2a:\u2009 \u03bdO8-H9(gas phase) [benzene] {dichloromethane}=(3691.9 cm-1) [3689.0 cm-1] {3687.4 cm-1} at the B3LYP\/6-31G(d) level and (3768.7 cm-1) [3767.1 cm-1] {3766.0 cm-1} at the B3LYP\/6-311+G(d, p) level; TS4a:\u2009 \u03bdO8-H9(gas phase) [benzene] {dichloromethane}=(3395.0 cm-1) [3426.2 cm-1] {3450.4 cm-1} at the B3LYP\/6-31G(d) level and (3453.4 cm-1) [3492.7 cm-1] {3519.7 cm-1} at the B3LYP\/6-311+G(d,p) level."},{"key":"jo048980jb00023\/jo048980jb00023_1","unstructured":"Aside from TSscis,anti,exo-6andtrans,anti,endo-7there are two more alternative TSs for anti attack, namely TSs cis,anti,endo and trans,anti,exo, deriving froms-cis-1ands-trans-1, respectively. We have already reported that B3LYP calculations indicate that TSs cis,anti,endo have higher free energies than theircis,anti,exo-6counterparts in the performic acid epoxidation of 2-cyclobutenol (by \u223c1.6\u22121.8 kcal\/mol)5band 2-cyclohexenol (by \u223c2.0\u22122.8 kcal\/mol)5dboth in the gas phase and in solution. In the case of 2-cyclopentenol epoxidation with performic acid, the TS cis,anti,endo is less stable than TScis,anti,exo-6bby 1.0 kcal\/mol (B3LYP\/6-31G(d)) and 1.5 kcal\/mol (B3LYP\/6-311+G(d,p)) both in the gas phase and in solution. As for TSs trans,anti,exo they reside at higher energy than the corresponding TSstrans,anti,endo-7and tend to transform into TSs cis,anti,endo by rotation of the formate moiety around the breaking O-\u2009-\u2009-O bond. Thus, the TS trans,anti,exo of the reaction of performic acid with 2-cyclopentenol could be located by using the B3LYP\/6-31G(d) method as implemented in TITAN but when this structure was optimized with Gaussian it afforded the TS cis,anti,endo."}],"container-title":["The Journal of Organic Chemistry"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jo048980j","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2021,10,4]],"date-time":"2021-10-04T11:02:01Z","timestamp":1633345321000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/doi\/10.1021\/jo048980j"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2004,9,25]]},"references-count":38,"journal-issue":{"issue":"22","published-print":{"date-parts":[[2004,10,1]]}},"alternative-id":["10.1021\/jo048980j"],"URL":"https:\/\/doi.org\/10.1021\/jo048980j","relation":{},"ISSN":["0022-3263","1520-6904"],"issn-type":[{"value":"0022-3263","type":"print"},{"value":"1520-6904","type":"electronic"}],"subject":[],"published":{"date-parts":[[2004,9,25]]}}}