Dar'in Dmitry, Kantin Grigory, Glushakova Daria, Sharoyko Vladimir, Krasavin Mikhail
Institute of Chemistry, Saint Petersburg State University, 26 Universitetsky prospekt, Peterhof 198504 Russia.
The Pavlov First Medical University, 6-8 Lva Tolstogo ulitsa, Saint Petersburg 197022, Russia.
J Org Chem. 2024 Jun 7;89(11):7366-7375. doi: 10.1021/acs.joc.2c02600. Epub 2023 Jan 5.
3-Diazotetramic acids were found to be valid substrates for the recently discovered approach toward natural-like Δ-spirobutenolides via Rh(II)-catalyzed O-H insertion into propiolic acids followed by base-promoted intramolecular Michael addition. The target Δ-spirobutenolides were obtained in generally high yields and, in the case of chiral 5-monosubstituted 3-diazotetramic acids, high diastereoselectivity. The synthesis of Δ-spirobutenolides that we report here was virtually insensitive to the structure of the propiolic acids though it was somewhat sensitive to the structure of the 3-diazotetramic acids, thereby demonstrating quite a large scope. Thus, a new class of α-diazocarbonyl compounds suitable for the realization of the approach outlined above was identified.
通过铑（II）催化的O-H插入到炔丙酸中，随后进行碱促进的分子内迈克尔加成，向天然样Δ-螺丁烯内酯的新发现方法中，3-重氮四酰胺被发现是有效的底物。目标Δ-螺丁烯内酯通常以高产率获得，并且在手性5-单取代的3-重氮四酰胺的情况下，具有高非对映选择性。我们在此报道的Δ-螺丁烯内酯的合成对炔丙酸的结构几乎不敏感，尽管它对3-重氮四酰胺的结构有些敏感，从而显示出相当广泛的范围。因此，确定了一类适用于实现上述方法的新型α-重氮羰基化合物。
