Hussain Waseem A, Parasram Marvin
Department of Chemistry, New York University, 29 Washington Pl, New York, New York 10003, USA.
Synthesis (Stuttg). 2024 Jun;56(11):1775-1786. doi: 10.1055/s-0042-1751534. Epub 2023 Dec 11.
Oxidative cleavage of alkenes leading to valuable carbonyl derivatives is a fundamental transformation in synthetic chemistry. In particular, ozonolysis is the mainstream method for the oxidative cleavage of alkenes that has been widely implemented in the synthesis of natural products and pharmaceutically relevant compounds. However, due to the toxicity and explosive nature of ozone, alternative approaches employing transition metals and enzymes in the presence of oxygen and/or strong oxidants have been developed. These protocols are often conducted under harsh reaction conditions that limit the substrate scope. Photochemical approaches can provide milder and more practical alternatives for this synthetically useful transformation. In this review, we outline recent visible-light-promoted oxidative cleavage reactions that involve photocatalytic activation of oxygen via electron transfer and energy transfer. Also, an emerging field featuring visible-light-promoted oxidative cleavage under anaerobic conditions is discussed. The methods highlighted in this review represent a transformative step toward more sustainable and efficient strategies for the oxidative cleavage of alkenes.
烯烃的氧化裂解生成有价值的羰基衍生物是合成化学中的一种基本转化反应。特别是,臭氧分解是烯烃氧化裂解的主流方法,已广泛应用于天然产物和药物相关化合物的合成中。然而,由于臭氧的毒性和易爆性,人们开发了在氧气和/或强氧化剂存在下使用过渡金属和酶的替代方法。这些方案通常在苛刻的反应条件下进行,限制了底物范围。光化学方法可为这种具有合成价值的转化反应提供更温和、更实用的替代方案。在本综述中,我们概述了最近可见光促进的氧化裂解反应,这些反应涉及通过电子转移和能量转移对氧进行光催化活化。此外,还讨论了一个新兴领域,即在厌氧条件下进行可见光促进的氧化裂解。本综述中强调的方法代表了朝着更可持续、更高效的烯烃氧化裂解策略迈出的变革性一步。