2006
DOI: 10.1002/ejoc.200500728
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Relay Propagation of Crowding: The Trifluoromethyl Group as Both an Emitter and Transmitter of Steric Pressure

Abstract: Whereas lithium 2,2,6,6-tetramethylpiperidide (LITMP) abstracts a proton exclusively from the 4-position of 3-bromobenzotrifluoride, the same base attacks selectively the 2-position when employed in the presence of N,N,NЈ,NЈЈ,NЈЈ-pentamethyldiethylenetriamine and potassium tert-butoxide ("Faigl mix"). 1-Bromo-3,5-bis(trifluoromethyl)benzene also undergoes metalation at the 2-position but [2-bromo-4-(trifluoromethyl)phenyl]silane does not react at all, evidently locked up by a C-SiR 3 /C-Br buttressing effect. … Show more

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Cited by 20 publications
(16 citation statements)
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“…As previously reported, [1][2][3] chlorine and bromine atoms are potent transmitters of the steric pressure emanating from an adjacent trialkylsilyl substituent. As we expected trifluoromethyl groups to behave similarly, we have selected three archetypical model compounds belonging to the benzotrifluoride family to verify this hypothesis.…”
Section: Introductionmentioning
confidence: 79%
“…As previously reported, [1][2][3] chlorine and bromine atoms are potent transmitters of the steric pressure emanating from an adjacent trialkylsilyl substituent. As we expected trifluoromethyl groups to behave similarly, we have selected three archetypical model compounds belonging to the benzotrifluoride family to verify this hypothesis.…”
Section: Introductionmentioning
confidence: 79%
“…In some cases (e.g. with X = SiMe 3 ), buttressing effects [34][35][36][37][38][39][40][41] (steric effects exerted by the X group through the fluoro group) 42 may compromise the reactivity of the 1,2-isomers 2. More importantly, the acidifying effect of substituents at meta positions is no longer the same as at ortho positions.…”
Section: Discussionmentioning
confidence: 99%
“…Hypotheses about its origin, nature and implications are still tentative. [15,16] To gain more insight, one first has to explore the scope of the phenomenon.…”
Section: Introductionmentioning
confidence: 99%