Department of Chemistry, Imperial College London, South Kensington, London, UK.
Nat Protoc. 2012 Oct;7(10):1765-73. doi: 10.1038/nprot.2012.095. Epub 2012 Sep 6.
The synthesis of Pd(OTf)(2)·2H(2)O is described. This was used to generate two different types of chiral dicationic palladium complexes for highly enantioselective addition of aromatic amines to α, β-unsaturated conjugate alkenes ([(R-BINAP)Pd(OH(2))(2)]OTf and (R-BINAP)Pd(μ-OH)OTf). The resulting optically active N-arylated β-amino acid derivatives are valuable synthetic intermediates for the synthesis of biologically active molecules and peptidomimetics. The reaction of (2E)-but-2-enoylcarbamate and aniline is shown as an example of the use of these catalysts for enantioselective aza-Michael addition. For the preparation of palladium(II) triflate, the time scale is 20 h 50 min, plus 5 h 15 min for the monomeric complex and plus 6 h 45 min for the dimeric complex.
Pd(OTf)(2)·2H(2)O 的合成。利用该方法生成了两种不同类型的手性二价钯配合物，用于高对映选择性地将芳基胺加成到α,β-不饱和共轭烯烃上([(R-BINAP)Pd(OH(2))(2)]OTf和(R-BINAP)Pd(μ-OH)OTf)。得到的光学活性 N-芳基化β-氨基酸衍生物是合成具有生物活性分子和肽模拟物的有价值的合成中间体。(2E)-丁-2-烯酰氨基甲酸酯和苯胺的反应被用作这些催化剂用于对映选择性氮杂-Michael 加成的示例。对于钯(II)三氟甲磺酸酯的制备，时间尺度为 20 小时 50 分钟，加上单体配合物的 5 小时 15 分钟，加上二聚体配合物的 6 小时 45 分钟。
