Electrospray ionization of methanolic solutions of p-hydroxyphenacyl derivatives HO-C(6)H(4)-C(O)-CH(2)-X (X = leaving group) provides abundant signals for the deprotonated species which are assigned to the corresponding phenolate anions (-)O-C(6)H(4)-C(O)-CH(2)-X. Upon collisional activation in the gas phase, these anions inter alia undergo loss of a neutral "C(8)H(6)O(2)" species concomitant with formation of the corresponding anions X(-). The energies required for the loss of the neutral roughly correlate with the gas phase acidities of the conjugate acids (HX). Extensive theoretical studies performed for X = CF(3)COO in order to reveal the energetically most favorable pathway for the formation of neutral "C(8)H(6)O(2)" suggest three different routes of similar energy demands, involving a spirocyclopropanone, epoxide formation, and a diradical, respectively.

Department of Organic Chemistry Faculty of Sciences Charles University Prague Hlavova 8 12083 Prague 2 Czech Republic

Zobrazit více v PubMed

Givens RS, Goeldner M, editors. Dynamic Studies in Biology: Phototriggers, Photoswitches, and Caged Biomolecules. Wiley; New York: 2005.

Givens RS, Weber JJF, Jung AH, Park C-H. In: Methods in Enzymology on “Caged Compounds: Chemistry, Instrumentation, and Applications”. Marriott G, editor. Vol. 291. 1998. p. 1.

Ma CS, Chan WS, Kwok WM, Yuo P, Phillips DL. J Phys Chem B. 2004;108:9264.

Ma CS, Zuo P, Kwok WM, Chan WS, Kan JTW, Toy PH, Phillips DL. J Org Chem. 2004;69:6641. PubMed

Ma CS, Kwok WM, Chan WS, Zuo P, Kan JTW, Toy PH, Phillips DL. J Am Chem Soc. 2005;127:1463. PubMed

Zuo P, Ma CS, Kwok WM, Chan WS, Phillips DL. J Org Chem. 2005;70:8661. PubMed

Ma CS, Kwok WM, Chan WS, Du Y, Kan JTW, Toy PH, Phillips DL. J Am Chem Soc. 2006;128:2558. PubMed

Chen XB, Ma CS, Kwok WM, Guan XG, Du Y, Phillips DL. J Phys Chem A. 2006;110:12406. PubMed

Wirz J. Chimia. 2007;61:638.

Chen XB, Ma CS, Kwok WM, Guan XG, Du Y, Phillips DL. J Phys Chem B. 2007;111:11832. PubMed

Ma CS, Kwok WM, Chan WS, Du Y, Zuo P, Kan JTW, Toy PH, Phillips DL. Curr Sci. 2009;97:202.

Cao Q, Guan X, George MW, Phillips DL, Ma CS, Kwok WM, Li MD, Du Y, Sun XZ, Xue JD. Faraday Disc. 2010;145:171.

Bucher G, Phillips DL, Schröder D, Carpenter B, Guthrie JP, Shaik S, Tahara T, Warshel A, Michl J, Williams I, Ashfold MNR, Pandey R, Meech SR, Misra R, Henchman RH, Hutchings GJ, Buurma NJ, Bain CD, Glowacki D, George MW, Pantos GD, Cramer CJ, Lloyd-Jones GC, Hunter CA, Varley LM, Hillman AR, Webb S, Philp D, Page MI. Faraday Disc. 2010;145:255.

Alcami M, Mó O, Yañez M. Mass Spectrom Rev. 2001;20:195. PubMed

Schwarz H. Int J Mass Spectrom. 2004;237:75.

Roithová J, Schröder D. Coord Chem Rev. 2009;253:666.

Roithová J, Schröder D. Chem Rev. 2010;110:1170. PubMed

Roithová J, Schröder D, Schwarz H. Angew Chem Int Ed. 2005;44:3092. PubMed

Roithová J, Schröder D. Int J Mass Spectrom. 2007;267:134.

Milko P, Roithová J, Schröder D, Lemaire J, Schwarz H, Holthausen MC. Chem Eur J. 2008;14:4318. PubMed

Milko P, Roithová J, Tsierkezos NG, Schröder D. J Am Chem Soc. 2008;130:7186. PubMed

Šrogl J, Hyvl J, Révész A, Schröder D. Chem Comun. 2009:3463. PubMed

Tsierkezos NG, Buchta M, Holý P, Schröder D. Rap Commun Mass Spectrom. 2009;23:1550. PubMed

Schröder D, Ducháčková L, Jušinski I, Eckert-Maksić M, Heyda J, Tůma L, Jungwirth P. Chem Phys Lett. 2010;490:14.

Révész A, Milko P, Žabka J, Schröder D, Roithová J. J Mass Spectrom. 2010;45:1246. PubMed

Zins EL, Pepe C, Schröder D. J Mass Spectrom. 2010;45:1253. PubMed

Aschi M, Harvey JN, Schalley CA, Schröder D, Schwarz H. J Chem Soc, Chem Commun. 1998:531.

Schröder D, Heinemann C, Schwarz H, Harvey JN, Dua S, Blanksby SJ, Bowie JH. Chem Eur J. 1998;4:2550.

Roithová J, Ricketts CL, Schröder D, Price SD. Angew Chem Int Ed. 2007;46:9316. PubMed

Feixas F, Ponec R, Schröder D, Roithová J, Fišer J, Price SD. J Phys Chem A. 2010;114:6681. PubMed

Givens RS, Stensrud K, Conrad PG, II, Yousef AL, Perera C, Senadheera SN, Heger D, Wirz J. Can J Chem. 2011 in press. PubMed PMC

Tintaru A, Roithová J, Schröder D, Charles L, Jušinski I, Glasovac Z, Eckert-Maksić M. J Phys Chem A. 2008;112:12097. PubMed

Cech NB, Enke CG. Mass Spectrom Rev. 2001;20:362. PubMed

Schröder D, Weiske T, Schwarz H. Int J Mass Spectrom. 2002;219:729.

Trage C, Diefenbach M, Schröder D, Schwarz H. Chem Eur J. 2006;12:2454. PubMed

O’Hair RAJ. Chem Commun. 2006:1469. PubMed

Armentrout PB. Int J Mass Spectrom. 2000;200:219.

Ervin KM. Chem Rev. 2001;101:391. PubMed

Narancic S, Bach A, Chen P. J Phys Chem A. 2007;111:7006. PubMed

Armentrout PB, Ervin KM, Rodgers MT. J Phys Chem A. 2008;112:10071. PubMed

O’Hair RAJ, Vrkic AK, James PF. J Am Chem Soc. 2004;126:12173. PubMed

Rodgers MT, Stanley JR, Amunugama R. J Am Chem Soc. 2000;122:10969.

Rannulu NS, Rodgers MT. J Phys Chem A. 2007;111:3465. PubMed

Than S, Maeda H, Irie M, Itoh S, Kikukawa K, Mishima K. J Phys Chem A. 2007;111:5988. PubMed

Schröder D, Engeser M, Brönstrup M, Daniel C, Spandl J, Hartl H. Int J Mass Spectrom. 2003;228:743.

Jagoda-Cwiklik B, Jungwirth J, Rulíšek L, Milko P, Roithová J, Lemaire J, Maitre P, Ortega JM, Schröder D. ChemPhysChem. 2007;8:1629. PubMed

Milko P, Roithová J, Schröder D, Lemaire J, Schwarz H, Holthausen MC. Chem Eur J. 2008;14:4318. PubMed

Tyo EC, Castleman AW, Jr, Schröder D, Milko P, Roithová J, Ortega JM, Cinellu MA, Cocco F, Minghetti G. J Am Chem Soc. 2009;131:13009. PubMed

Gaussian 03, Revision E.01. Gaussian, Inc; Wallingford CT: 2004.

Dunning TH., Jr J Chem Phys. 1989;90:1007.

Photoremovable protecting groups in chemistry and biology: reaction mechanisms and efficacy