Enantio- and diastereoselective hetero-Diels–Alder reactions between 4-methyl-substituted Rawal’s diene and aldehydes catalyzed by chiral dirhodium(II) carboxamidates: catalytic asymmetric synthesis of (−)-cis-aerangis lactone
作者:Yudai Watanabe、Naoyuki Shimada、Masahiro Anada、Shunichi Hashimoto
DOI:10.1016/j.tetasy.2013.10.016
日期:2014.1
The first catalytic asymmetric hetero-Diels–Alder (HDA) reaction between 3-tert-butyldimethylsilyloxy-1-dimethylamino-1,3-pentadiene (4-methyl-substituted Rawal’s diene) and aldehydes is described. With 3 mol % of dirhodium(II) tetrakis[N-benzene-fused-phthaloyl-(S)-piperidinonate], Rh2((S)-BPTPI)4, the cycloaddition reaction proceeded exclusively in an endo fashion and gave, after a novel sequential
描述了3-叔丁基二甲基甲硅烷氧基-1-二甲基氨基-1,3-戊二烯(4-甲基取代的拉瓦尔二烯)和醛之间的第一个催化不对称杂狄尔斯-阿尔德(HDA)反应。用3mol%的四[ N-苯-稠合邻苯二甲酰基-(S)-哌啶子酸酯]的铑(II),Rh 2((S)-BPTPI)4,环加成反应仅以内消旋方式进行,然后得到乙炔二甲酸二甲酯和乙酰氯的新的序贯治疗,相应的2,3-顺式-双取代的二氢吡喃酮,具有高达98%的ee和完美的非对映选择性。(-)-顺式-aerangis内酯的不对称合成证明了该催化方案的实用性。