- A route to 2-alkenyl-3-(tert-butyldiphenylsilyl)amines and application to the construction of a tricyclic ring system
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N-Tosyl 3,3-dialkyl-2-(tert-butyldiphenylsilylmethyl)azetidines rearrange smoothly into the corresponding 2-alkenyl-3-(tert-butyldiphenylsilyl)amines upon exposure to BF3·OEt2 in CH2Cl 2. The reaction involves sequential σC-N bond cleavage, 1,2-migration of the N-tosyl-aminomethyl group, and deprotonation of the resultant tert-carbenium ions. For the instance in which the carbenium ion formed from migration of the N-tosyl-aminomethyl group is highly stable by virtue of being, for example, tertiary as well as benzylic, the migration takes place in sync with σC-N bond cleavage, which leads to high configurational control at the tert-butyldiphenylsilylmethyl-bearing carbon atom in the product. In contrast to N-tosyl-substituted 3-alkyl-2-(tert- butyldiphenylsilylmethyl)azetidine, the corresponding 3,3-dialkyl derivative rearranges into N-tosyl-2-alkenyl-3-(tert-butyldiphenylsilyl)amine upon exposure to BF3·OEt2. The reaction involves sequential σC-N bond cleavage, 1,2-migration of the N-tosyl-aminomethyl group, and deprotonation of the resultant tert-carbenium ion. Copyright
- Yadav, Veejendra K.,Narhe, Bharat D.,Kumar, Kamlesh,Hulikal, Vijaykumar
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p. 4163 - 4174
(2013/07/19)
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- The Reaction of tert-Butyldiphenylsilylcuprates with Allenes
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Bis(tert-butyldiphenylsilyl)cuprate 1 reacts with allenes to form allyl- and vinyl-silanes.With allene itself the cuprate reagent shows a different regiochemistry from that of bis(phenyldimethylsilyl)cuprate.The regiochemistry can be controlled by choosing an appropriate reaction temperature.The intermediate cuprate 4 resulting from the addition of 1 to allene reacts with a wide variety of electrophiles giving functionalised allylsilanes.Phenylallenes isomerise to acetylenes.
- Barbero, Asuncion,Cuadrado, Purificacion,Gonzalez, Ana M.,Pulido, Francisco J.,Fleming, Ian
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p. 2811 - 2816
(2007/10/02)
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