Conflict of interests The authors declare no competing financial interests.
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Gas-phase carbanion rearrangements. Does the Wittig rearrangement occur for deprotonated vinyl ethers?
作者:Peter C. H. Eichinger、John H. Bowie
DOI:10.1039/p29900001763
日期:——
Deprotonation of alkyl vinyl ethers (CH2CHOR) with NH2– in the gas phase yields the two carbanions CH2OR and –CHCHOR. The former ion can be synthesized specifically using the SN2(Si) reaction CH2C(SiMe3)OR + NH2–→CH2OR + Me3SiNH2: the ion undergoes several competitive and characteristic collision-induced reactions. For example, (i) when R Et, elimination of an alkene, i.e. CH2OR→(CH2CHO)–+(R–H), and
Tandem Inter [4 + 2]/Intra [3 + 2] Cycloadditions of Nitroalkenes. The Bridged Mode (β-Tether)
作者:Scott E. Denmark、Julie A. Dixon
DOI:10.1021/jo9802168
日期:1998.9.1
A new variation of the tandem inter [4 + 2]/intra [3 + 2] cycloaddition of nitroalkenes has been developed. This method involves the Lewis acid-promoted [4 + 2] cycloaddition of nitro olefins 12 with 1-alkoxy-1,4-dienes 3. The resulting nitronates 13, bearing a C(5) tethered dipolarophile, undergo thermal, intramolecular [3 + 2] cycloaddition to afford stable tricyclic nitroso acetals 14, which can