Abstract
A method for the investigation of diastereoselective effects in reactions of gaseous ions bearing flexible backbones is described. It relies on the study of diastereoselectively labeled substrates that are studied by contemporary mass spectrometric means. While most examples discussed here deal with bond activations mediated by bare transition-metal ions in the gas phase, it is shown that the method is not restricted to this particular chemistry. Interestingly, the reason why transition-metal ions show relatively pronounced diastereoselective effects is that the activation barriers associated with their reactions are sufficiently small to be influenced by even subtle steric modifications of the substrate. Provided that suitable isotopically labeled precursors are investigated, even complex mechanistic schemes including competing side reactions can be analyzed by kinetic modeling of the isotope distributions in the reaction products.
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9 References
Splitter JS, Turecek F (eds) (1994) Applications of mass spectrometry to organic stereochemistry. VCH, Weinheim
Mandelbaum A (1994) In: Splitter JS, Turecek F (eds) Applications of mass spectrometry to organic stereochemistry. VCH, Weinheim, p 299, and numerous references therein
Reetz MT (2002) Angew Chem 114:1391; Angew Chem Int Ed 41:1335
Guo J, Wu J, Siuzdak G, Finn MG (1999) Angew Chem 111:1868; Angew Chem Int Ed 38:1754
Reetz MT, Becker MH, Kleim H-W, Stöckigt D (1999) Angew Chem 111:1872; Angew Chem Int Ed 38:1758
Winkler FJ, Splitter JS (1994) In: Splitter JS, Turecek F (eds) Applications of mass spectrometry to organic stereochemistry. VCH, Weinheim, p 353
Fales HM, Wright GJ (1977) J Am Chem Soc 99:2339
Selva A, Redenti E, Amari G, Ventura P (1992) Org Mass Spectrom 27:63
Splitter JS (1994) In: Splitter JS, Turecek F (eds) Applications of mass spectrometry to organic stereochemistry. VCH, Weinheim, p 83
Audier HE, Felkin H, Fetizon M, Vetter W (1965) Bull Soc Chim Fr 3236
Morizur JP, Taphanel MH, Mayer PS, Morton TH (2000) J Org Chem 65:381
Eller K, Schwarz H (1991) Chem Rev 91:1121
Seemeyer K, Schröder D, Kempf M, Lettau O, Müller J, Schwarz H (1995) Organometallics 14:4465
Huang Y, Profilet RD, Ng JH, Ranasinghe YA, Rothwell IP, Freiser BS (1994) Anal Chem 66:1050
Freiser BS (1994) Acc Chem Res 27:353
Schwarz H (1989) Acc Chem Res 22:282
Breslow R (1972) Chem Soc Rev 1:553; (1980) Acc Chem Res 13:170
Schröder D, Schwarz H (1993) J Am Chem Soc 115:8818
Schröder D, Zummack W, Schwarz H (1994) J Am Chem Soc 116:5857
Loss J, Schröder D, Zummack W, Schwarz H (2002) Int J Mass Spectrom 217:169
Hornung G (1998) Regio-and stereochemistry in the transition-metal mediated remote functionalization in the gas phase. Verlag Dissertation.de, Berlin
Hornung G, Schröder D, Schwarz H (1995) J Am Chem Soc 117:8192
Hässelbarth A, Prüsse T, Schwarz H (1990) Chem Ber 123:213
Hornung G, Schröder D, Schwarz H (1997) J Am Chem Soc 119:2273
Schalley CA, Hornung G, Schröder D, Schwarz H (1998) Int J Mass Spectrom Ion Processes 172:181
Schalley CA, Hornung G, Schröder D, Schwarz H (1998) Chem Soc Rev 27:91
Hornung G, Schalley CA, Dieterle M, Schröder D, Schwarz H (1997) Chem Eur J 3:1866
Trage C, Zummack W, Schröder D, Schwarz H (2001) Angew Chem 113:2780; Angew Chem Int Ed 40:2708
Thibblin A, Ahlberg P (1989) Chem Soc Rev 18:209
Loos J, Schröder D, Zummack W, Schwarz H, Thissen R, Dutuit O (2002) Int J Mass Spectrom 214:105
Seemeyer K, Prüsse T, Schwarz H (1993) Helv Chim Acta 76:1632
Prüsse T, Fiedler A, Schwarz H (1991) Helv Chim Acta 74:1127
Semialjac M, Loos J, Schröder D, Schwarz H (2002) Int J Mass Spectrom 214:129
Loos J, Schröder D, Semialjac M, Weiske T, Schwarz H, Höhne G, Thissen R, Dutuit O (2002) Int J Mass Spectrom 214:155
Loss J (2000) Diplomarbeit. TU Berlin
Smith MB, March J (2001) March’s advanced organic chemistry, 5th edn. Wiley, New York, p 524
Green MM, Boyle BA, Varaimani M, Mukhopadhyay T, Saunders WH Jr, Bowen P, Allinger NL (1986) J Am Chem Soc 108:2381
Schröder D (1992) Dissertation. TU Berlin D83
Prüsse T, Schwarz H (1989) Organometallics 8:2856
Nikolaev EN, Goginashvili GT, Tal’rose VL, Kostyanovsky RG (1988) Int J Mass Spectrom Ion Processes 86:249
Filippi A, Giardini A, Piccirillo S, Speranza M (2000) Int J Mass Spectrom 198:137
Lebrilla CB (2001) Acc Chem Res 34:653
Schalley CA (2000) Int J Mass Spectrom 194:11
Schalley CA (2001) Mass Spectrom Rev 20:253
Schalley CA, Weis P (2002) Int J Mass Spectrom 221:9–19
Trage C, Schröder D, Schwarz H (2003) Organometallics 22:693
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Schröder, D., Schwarz, H. (2003). Diastereoselective Effects in Gas-Phase Ion Chemistry. In: Schalley, C.A. (eds) Modern Mass Spectrometry. Topics in Current Chemistry, vol 225. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-36113-8_4
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DOI: https://doi.org/10.1007/3-540-36113-8_4
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