EaStCHEM School of Chemistry, University of Edinburgh, Joseph Black Building, David Brewster Road, Edinburgh EH9 3FJ, United Kingdom.
Org Lett. 2021 May 7;23(9):3248-3252. doi: 10.1021/acs.orglett.1c00620. Epub 2021 Apr 15.
The development of the first enantioselective -Claisen rearrangement has been achieved. Using a chiral aluminum Lewis acid, illicinole is rearranged to give (-)-illicinone A (er 87:13), which can then be converted into more complex -derived prenylated phenylpropanoids. The absolute configurations of the natural products (+)-cycloillicinone and (-)-illicarborene A have been determined, and our results cast doubt on the enantiopurity of the natural samples.
首例对映选择性-Claisen重排反应已经实现。采用手性铝路易斯酸,使亚麻苦苷发生重排,得到(-)-胡椒烯酮 A(er 87:13),然后可以将其转化为更复杂的 -衍生的芳基丙二烯类化合物。天然产物(+)-环胡椒烯酮和(-)-胡椒烯 A 的绝对构型已确定,我们的结果对天然样品的对映体纯度提出了质疑。