A direct amidation of carboxylicacids with tertiary amines could be carried out in the presence of the Ph3P–I2 activator. With an appropriate reagent addition sequence, a range of carboxylicacids including aliphatic, allylic, and aromatic acids could be converted into their corresponding tertiary amides under mild conditions without requirement of metal catalysis.
The direct α‐siladifluoromethylation of lithiumenolates with the Ruppert–Prakash reagent (CF3TMS) is shown to construct the tertiary and quaternary carbon centers. The Ruppert–Prakash reagent, which is versatile for various trifluoromethylation as a trifluoromethyl anion (CF3−) equivalent, can be employed as a siladifluoromethyl cation (TMSCF2+) equivalent by CFbondactivation due to the strong
Metal-Free Formal Oxidative C−C Coupling by In Situ Generation of an Enolonium Species
作者:Daniel Kaiser、Aurélien de la Torre、Saad Shaaban、Nuno Maulide
DOI:10.1002/anie.201701538
日期:2017.5.15
contemporary organic synthesis relies on transformations that are driven by the intrinsic, so‐called “natural”, polarity of chemical bonds and reactive centers. The design of unconventionally polarized synthons is a highly desirable strategy, as it generally enables unprecedented retrosynthetic disconnections for the synthesis of complex substances. Whereas the umpolung of carbonyl centers is a well‐known