Department of Chemistry, University College London, 20 Gordon Street, London, WC1H OAJ, UK.
Org Biomol Chem. 2013 Nov 14;11(42):7301-17. doi: 10.1039/c3ob41632a.
In this report, a thorough evaluation of the use of aerobically initiated, metal-free hydroacylation of various C=C and N=N acceptor molecules with a wide range of aldehydes is presented. The aerobic-activation conditions that have been developed are in sharp contrast to previous conditions for hydroacylation, which tend to use transition metals, peroxides that require thermal or photochemical degradation, or N-heterocyclic carbenes. The mildness of the conditions enables a number of reactions involving sensitive reaction partners and, perhaps most significantly, allows for α-functionalised chiral aldehydes to undergo radical-based hydroacylation with complete retention of optical purity. We also demonstrate how the resulting hydroacylation products can be transformed into other useful intermediates, such as γ-keto-sulfonamides, sultams, sultones, cyclic N-sulfonyl imines and amides.
在本报告中，我们对使用有氧引发的、无金属的氢酰化反应，将各种 C=C 和 N=N 受体分子与广泛的醛类进行反应，进行了全面评估。所开发的有氧激活条件与以前的氢酰化条件形成鲜明对比，以前的条件往往需要使用过渡金属、需要热或光降解的过氧化物，或 N-杂环卡宾。这些温和的条件使得许多涉及敏感反应伙伴的反应成为可能，也许最重要的是，允许α-官能化的手性醛与完全保留光学纯度的自由基氢酰化反应。我们还展示了如何将所得的氢酰化产物转化为其他有用的中间体，如γ-酮磺酰胺、琥珀酰胺、琥珀酮、环状 N-磺酰亚胺和酰胺。
