Ouellette Erik T, Lougee Marshall G, Bucknam Andrea R, Endres Paul J, Kim John Y, Lynch Emma J, Sisko Elizabeth J, Sculimbrene Bianca R
Department of Chemistry, College of the Holy Cross, 1 College Sreet, Worcester, Massachusetts 01610, United States.
J Org Chem. 2021 Jun 4;86(11):7450-7459. doi: 10.1021/acs.joc.1c00414. Epub 2021 May 17.
The desymmetrization of ten prochiral diols by phosphoryl transfer with a titanium-BINOLate complex is discussed. The phosphorylation of nine 1,3-propane diols is achieved in yields of 50-98%. Enantiomeric ratios as high as 92:8 are achieved with diols containing a quaternary C-2 center incorporating a protected amine. The chiral ligand, base, solvent, and stoichiometry are evaluated along with a nonlinear effect study to support an active catalyst species that is oligomeric in chiral ligand. The use of pyrophosphates as the phosphorylating agent in the desymmetrization facilitates a user-friendly method for enantioselective phosphorylation with desirable protecting groups (benzyl, -nitrobenzyl) on the phosphate product.
本文讨论了用钛-联萘酚配合物通过磷酰基转移对十种前手性二醇进行去对称化反应。九种1,3-丙二醇的磷酸化反应产率为50-98%。对于含有带有保护胺的季碳C-2中心的二醇，对映体比例高达92:8。对手性配体、碱、溶剂和化学计量比进行了评估，并开展了非线性效应研究，以支持在 chiral ligand 中呈低聚态的活性催化剂物种。在去对称化反应中使用焦磷酸盐作为磷酰化剂，为在磷酸盐产物上带有理想保护基团（苄基、对硝基苄基）的对映选择性磷酸化提供了一种用户友好的方法。
