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Tetrahedron
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Sherrill, W.M.1
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44
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79957756163
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See the Supporting Information for details
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See the Supporting Information for details.
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47
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79957777084
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For an account on the reactivity of mesityl-substituted triazolium salts
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For an account on the reactivity of mesityl-substituted triazolium salts, see: Chiang, P.-C.; Bode, J. W. TCI Mail 2011, 149, 2
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TCI Mail
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Chiang, P.-C.1
Bode, J.W.2
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48
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79957780100
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Linear and branched aliphatic aldehydes did not undergo the hydroacylation reaction, affording only traces of the desired product along with the nearly quantitative formation of acyloin even under more forcing conditions (20 mol% of catalyst at 80 °C)
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Linear and branched aliphatic aldehydes did not undergo the hydroacylation reaction, affording only traces of the desired product along with the nearly quantitative formation of acyloin even under more forcing conditions (20 mol% of catalyst at 80 °C).
-
-
-
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49
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79957676086
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Attempts to improve the yield or diastereoselectivity by varying the temperature of the reaction proved ineffective
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Attempts to improve the yield or diastereoselectivity by varying the temperature of the reaction proved ineffective.
-
-
-
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50
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0035936747
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Only product 3g is previously reported in the literature
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Only product 3g is previously reported in the literature: Nishimura, T.; Ohe, K.; Uemura, S. J. Org. Chem. 2001, 66, 1455
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Nishimura, T.1
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0035077764
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Auricchio, S.; Grassi, S.; Malpezzi, L.; Sarzi Sartori, A.; Truscello, A. M. Eur. J. Org. Chem. 2001, 1183
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Auricchio, S.1
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Truscello, A.M.5
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52
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79957705575
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Substrates with a combination of electron-richness and steric hindrance gave little amount of the desired product. For example, 2-methoxybenzaldehyde showed less than 20% conversion with 20 mol% of the triazolium catalyst (data not shown)
-
Substrates with a combination of electron-richness and steric hindrance gave little amount of the desired product. For example, 2-methoxybenzaldehyde showed less than 20% conversion with 20 mol% of the triazolium catalyst (data not shown).
-
-
-
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53
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79957681564
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This result is consistent with our observation that electron-rich aldehydes exhibit lower reactivity
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This result is consistent with our observation that electron-rich aldehydes exhibit lower reactivity.
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54
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79957752909
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This is consistent with our hypothesis on the origin of diastereoselectivity, vide infra. See refs 30 and 31
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This is consistent with our hypothesis on the origin of diastereoselectivity, vide infra. See refs 30 and 31.
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55
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79957669334
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3 showed no detectable formation of the hydroacylated product 3a, see ref 15
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3 showed no detectable formation of the hydroacylated product 3a, see ref 15.
-
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57
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79957746226
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It amounted to only 85%, most likely due to scrambling with the proton of triazolium salt 7a in the equilibrating process between benzoin and retro-benzoin
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It amounted to only 85%, most likely due to scrambling with the proton of triazolium salt 7a in the equilibrating process between benzoin and retro-benzoin.
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58
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49649083861
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Prepared by adapting a known procedure: Alnasleh, B. K.; Sherrill, W. M.; Rubin, M. Org. Lett. 2008, 10, 3231 See Supporting Information for more details and complete characterization
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Alnasleh, B.K.1
Sherrill, W.M.2
Rubin, M.3
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59
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0001289430
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Because cyclopropyl anions are observed to be configurationally stable (see;;), anti -deuterium incorporation would have been observed based on a stepwise mechanism. (8b) Alternatively, it is also possible that, in a stepwise addition process, formation of the negative charge occurs syn to the Breslow intermediate for electrostatic stabilization. The corresponding stepwise mechanism therefore cannot at this point be excluded
-
Because cyclopropyl anions are observed to be configurationally stable (see Walborsky, H. M.; Impastato, F. J.; Young, A. E. J. Am. Chem. Soc. 1964, 86, 3283), anti -deuterium incorporation would have been observed based on a stepwise mechanism. (8b) Alternatively, it is also possible that, in a stepwise addition process, formation of the negative charge occurs syn to the Breslow intermediate for electrostatic stabilization. The corresponding stepwise mechanism therefore cannot at this point be excluded
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0028225158
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For related noncatalytic additions to electron-neutral alkenes proceeding through a five-membered concerted transition state, see: Oppolzer, W.; Spivey, A. C.; Bochet, C. G. J. Am. Chem. Soc. 1994, 116, 3139
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0023043811
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For discussions on the hyperconjugative stabilization in addition reactions
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For discussions on the hyperconjugative stabilization in addition reactions, see: Houk, K.; Paddon-Row, M.; Rondan, N.; Wu, Y.; Brown, F.; Spellmeyer, D.; Metz, J.; Li, Y.; Loncharich, R. Science 1986, 231, 1108
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