TAILIEUCHUNG - Organocatalysis Episode 10

Tham khảo tài liệu 'organocatalysis episode 10', kỹ thuật - công nghệ, cơ khí - chế tạo máy phục vụ nhu cầu học tập, nghiên cứu và làm việc hiệu quả | Enantioselective Photochemistry 261 1. BuLi - -CICOOMenthyl THF 2. separation of diastereoisomers 3. TFA neat 41 81 -12 - -12 Scheme 4. aromatic naphthyl shield either provided no acceptable differentiation of the prochiral planes or turned out to be unstable under the irradiation conditions due to unfavourable long wavelength absorptions. With the face differentiation provided by the templates -12 and - -12 being virtually complete the remaining decisive factor for the extent of chirality transfer is the amount of substrate actually being bound to the template when the reaction takes place. While -12 or - -12 cannot form hydrogen bond-mediated dimers with themselves if they are enantiomerically pure dimerisation of the substrate Kdim is always to be considered as a competing process to host-guest complexation Kass . To favour hydrogen-bond mediated complexations reactions using templates -12 or - -12 are generally performed in non-polar solvents . toluene at low temperature . -60 C with greater than a one-fold excess of the template. While the first two conditions are beneficial for hydrogen bonding in general the excess of template serves to ensure maximum substrate complexation in contrast to substrate dimeri-sation. However even in cases where substrate dimerisation is consider 262 S. Breitenlechner P. Selig T. Bach ably stronger than complexation to the template . Kdim Kass com-plexation is always favoured over dimerisation enthalpically. High ee values could thus be achieved even in reactions using substrates with unfavourable dimerisation behaviour Selig and Bach 2006 . Although the use of an excess of template may seem uneconomical at first it is important to note that templates -12 and - -12 being photochemi-cally unreactive themselves can be recovered from the reaction mixture generally in yields between 80 and 99 and used repeatedly. 2 2 -Photocycloaddition Reactions As the synthetically most useful and most frequently used photochemical .

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