Uracil-Cu(I) Catalyst: Allylation of Cyclopropanols with Morita-Baylis-Hillman Alcohols under Water-tolerant Conditions

Jingwei Hou,^aXiaohong Li,^aKaiyu Yan,^aLei Zhang,^*bTeck-Peng Loh^*c,dand Peizhong Xie^*a

^aSchool of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, P. R. China.

^bSchool of Science, Tianjin Chengjian University, Tianjin 300384, China.

^cCollege of Advanced Interdisciplinary Science and Technology, Henan University of Technology, Zhengzhou, 450001, China.

^dDivision of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371.

Abstract:Inspired by the high affinity of copper with DNA and RNA, a uracil-copper catalytic system was developed to promote ring-opening allylation of cyclopropanols with allylic alcohols under water-tolerant conditions. A new C-OH bond-breaking model can well resolve the trade-off between the need for acidic activators for C(allyl)-OH bond cleavage and the demand for strong basic conditions for generating homoenolates. Therefore, Morita-Baylis-Hillman alcohols, rather than pre-activated versions, could be incorporated directly into dehydrative cross-coupling with cyclopropanols delivering water as the only by-product. A variety of functionalized δ,ε-unsaturated ketones were obtained in good to high yield with high E-selectivity.

Chemical Science2023, doi.org/10.1039/D3SC04890J.（影响因子：8.4）

论文链接：https://pubs.rsc.org/en/content/articlelanding/2023/sc/d3sc04890j