酸盐与酸盐的化以制备通过Csp-Csp2 Bond Cleavage的功能化[1,4]Oxazinones
Yu Zhao1, Li-Bing Yan1, Lin-Fen Liao1
1State Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources, Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education of China), Collaborative Innovation Center for Guangxi Ethnic Medicine, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, 15 Yu Cai Road, Guilin 541004, China.
这项研究引入了一种新方法,使用高价 (III) 化合物在和中切割多重键,形成具有高选择性和产量的功能化[1,4]oxazinones.
科学领域:
- 有机化学 有机化学
- 合成化学 合成化学
- 催化剂是一种催化剂.
背景情况:
- 超价化合物是有机合成中的多功能试剂.
- 选择性裂变和碳-碳和碳-异原子键的形成对于构建复杂分子至关重要.
- 和是有机合成中的重要组成部分.
研究的目的:
- 为功能化[1,4]oxazinones开发一种新的合成策略.
- 为了实现选择性的Csp-Csp2,C=N和N-O键裂和重组.
- 为了创建具有高 diastereoselectivity 的邻近碳立体中心.
主要方法:
- 过高价值的 (III) 化合物介导反应.
- 多米诺反应序列包括 [4+3] 循环加法,重新排列,循环化和 dearomatization/rearomatization.
- 一合成方法. 一合成方法.
主要成果:
- 有效合成各种功能化的[1,4]oxazinones.
- 实现了高产量和多重选择性.
- 已证明具有广泛的基质范围和良好的功能组耐受性.
结论:
- 开发的方法为[1,4]oxazinones提供了一条新且高效的途径.
- 反应通过复杂的多米诺机制进行.
- 这一策略使多种债券类型的同时分拆和再组合成为可能.
相关概念视频
Alkynes to Carboxylic Acids: Oxidative Cleavage
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Preparation of Alkynes: Alkylation Reaction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
Oxidative Cleavage of Alkenes: Ozonolysis
Ozone is a symmetrical bent molecule stabilized by a resonance structure.
Preparation of Alkynes: Dehydrohalogenation
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
Electrophilic Addition to Alkynes: Halogenation
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.


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