Application of Propargylic Radicals in Organic Synthesis

doi:10.6023/A19060201

Acta Chimica Sinica ›› 2019, Vol. 77 ›› Issue (9): 803-813.DOI: 10.6023/A19060201 Previous Articles Next Articles

Special Issue: 有机自由基化学

Review

炔丙基自由基在有机合成化学中的应用

路福东^a, 姜烜^a, 陆良秋^a^*(), 肖文精^a^b^*()

^a华中师范大学化学学院农药与化学生物学教育部重点实验室武汉 430079
^b中国科学院上海有机化学研究所金属有机化学国家重点实验室上海 200032

投稿日期:2019-06-08 发布日期:2019-08-13
通讯作者: 陆良秋,肖文精 E-mail:luliangqiu@mail.ccnu.edu.cn;wxiao@mail.ccnu.edu.cn
作者简介:路福东, 1995年出生于山东安丘, 2017年在华中农业大学获得学士学位, 目前在肖文精教授和陆良秋教授指导下攻读硕士学位. 研究兴趣是可见光催化的不对称反应.|姜烜, 1994年出生于浙江江山, 2016年在武汉理工大学获得学士学位, 目前在肖文精教授和陆良秋教授指导下攻读硕士学位. 研究兴趣是可见光催化的脱氨基偶联反应.|陆良秋教授1982年出生于浙江绍兴, 2005年和2011年在华中师范大学化学学院先后获得学士和博士学位(导师: 肖文精教授), 随后留校工作. 2011年至2013年以洪堡学者身份赴德国莱布尼茨催化所Matthias Beller教授课题组进行博士后研究. 2015年6月, 破格晋升为教授. 其研究兴趣主要是过渡金属催化的偶极环化反应与可见光促进的有机光化学合成研究.|肖文精教授1965年出生于湖北公安, 1984年和1990年在华中师范大学化学系先后获得学士和硕士学位. 1997年至2000年在加拿大渥太华大学化学系学习并获得博士学位(导师: Howard Alper教授). 2001年至2002年在美国加州理工学院化学与化学工程系David W. C. MacMillan教授课题组从事博士后研究. 2003年加入华中师范大学化学学院. 其研究兴趣主要是发展新的方法学合成具有潜在生物活性的碳杂环化合物.
基金资助:
项目受国家自然科学基金(Nos. 21572074);项目受国家自然科学基金(21772052);项目受国家自然科学基金(21772053);湖北省自然科学基金资助(Nos. 2015CFA033);湖北省自然科学基金资助(2017AHB047)

Application of Propargylic Radicals in Organic Synthesis

Lu, Fu-Dong^a, Jiang, Xuan^a, Lu, Liang-Qiu^a^*(), Xiao, Wen-Jing^a^b^*()

^aKey Laboratory of Pesticide & Chemical Biology Ministry of Education and College of Chemistry, Central China Normal University, Wuhan 430079
^bState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032

Received:2019-06-08 Published:2019-08-13
Contact: Lu, Liang-Qiu,Xiao, Wen-Jing E-mail:luliangqiu@mail.ccnu.edu.cn;wxiao@mail.ccnu.edu.cn
Supported by:
Project supported by the National Natural Science Foundation of China(Nos. 21572074);Project supported by the National Natural Science Foundation of China(21772052);Project supported by the National Natural Science Foundation of China(21772053);the Natural Science Foundation of Hubei Province(Nos. 2015CFA033);the Natural Science Foundation of Hubei Province(2017AHB047)

The production and transformation of alkynes occupys an important position in organic synthetic chemistry. Within this realm, propargylic functionalization of alkynes is a feasible way towards this purpose. Especially, the propargylic functionalization via radical pathways has flourished in the last decade, which is believed to be a significant complement to the classic metal-catalyzed propargylation reaction involving cationic intermediates. According to the reaction modes, these advancements will be highlighted by classifying into four types. The first one is the propargylic functionalization reactions involving propargylic radicals. Generally, propargylic radicals can be generated through single electron reduction of alkyne substrates by low-valence metal catalysts or excited state of photocatalysts, then participated in the following cross-coupling reactions to achieve alkyne products. In this part, asymmetric variants have been also well developed. The second one is the preparation of allene compounds through the allenyl radical pathway. For these processes, propargylic radicals can isomerize to allenyl radicals, which can participate in the copper- or nickel-catalyzed coupling reaction to produce significant allene compounds. The third one is the dehydrative alkylation reaction of propargyl alcohols that involve propargylic radical intermediates, too. Such radical intermediates can be further oxidized to propargylic cation intermediates, followed by a deprotonation to form substituted 1,3-enyne compounds. The forth one is the synthesis of vinylic alkoxyamines through a propargylic radical route. Initially, propargyl alcohols can be converted to propargylic radical species by the joint action of copper catalysts and TEMPO. The generated propargylic radical species can be captured by TEMPO to form vinylic alkoxyamines. Finally, an outlook on the radical propargylic functionalizations will be provided at the end of this review.

Key words: propargylic radical, propargylic functionalization, alkyne, allene, transition metal catalysis

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Lu, Fu-Dong, Jiang, Xuan, Lu, Liang-Qiu, Xiao, Wen-Jing. Application of Propargylic Radicals in Organic Synthesis[J]. Acta Chimica Sinica, 2019, 77(9): 803-813.

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Fig. & Tab. 20

Figure 1. Transformations of propargylic radicals (FG: functional group)

Figure 2. Kharasch-type propargylic C—H bond oxidation

Figure 3. Nickel-catalyzed asymmetric propargylic arylations

Figure 4. Catalytic asymmetric synthesis of a potent dihydrofolate reductase inhibitor

Figure 5. Mechanism of the Nickel-catalyzed propargylic arylation

Figure 6. Iron-catalyzed propargylic alkylations

Figure 7. Iron-catalyzed propargylic arylations

Figure 8. Asymmetric propargylic cyanation enabled by synergetic photoredox and copper catalysis

Figure 9. Copper- and cobalt-catalyzed peroxidation-oxyalkylation reactions of 1,3-enynes

Figure 10. Copper-catalyzed oxidation reactions of 1,3-enynes

Figure 11. Copper-catalyzed peroxidation reactions of 1,3-enynes

Figure 12. Iron-catalyzed peroxidation-carbamylation reactions of 1,3-enynes

Figure 13. Isomerization of propargylic radical to allene radical initiated by AIBN

Figure 14. Nickel-catalyzed 1,4-difunctionalization of 1,3-enynes

Figure 15. Copper-catalyzed 1,2- and 1,4-difunctionalization of 1,3-enynes

Figure 16. Copper-catalyzed 1,4-difunctionalization of 1,3-enynes

Figure 17. Copper-catalyzed 1,4-alkylarylation of 1,3-enynes

Figure 18. Nickel-catalyzed 1,4-difunctionalization of 1,3-enynes

Figure 19. Iron-catalyzed dehydrative alkylation of propargyl alcohols

Figure 20. Copper-catalyzed synthesis of vinyl alkoxylamines

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炔丙基自由基在有机合成化学中的应用

Application of Propargylic Radicals in Organic Synthesis

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