氧气引发的硫中心自由基参与的构建S—S、P—S和C—S键研究进展

doi:10.6023/cjoc202105015

摘要/Abstract

含硫有机化合物广泛应用于有机合成、医药、农药和功能材料等领域中, 发展绿色、温和、高效的有机硫化合物的合成方法具有重要意义. 作为理想的绿色氧化剂, 氧气可直接引发一些含硫化合物为硫中心自由基, 其参与的反应为构建S—S、P—S和C—S键提供了新途径. 该方法可避免使用毒性试剂、过渡金属和强氧化剂等, 而且反应条件温和. 依据反应类型的不同, 对近年来氧气引发的硫中心自由基参与的构建S—S、P—S和C—S键研究进展进行介绍.

关键词: 氧气, 硫中心自由基, 有机硫化合物, 自由基反应

Sulfur-containing organic compounds have been widely used in organic synthesis, pharmaceuticals, pesticides and functional materials. Thus, the development of green, mild and highly efficient methodologies for the synthesis of organosulfur compounds is of great importance. Some sulfur-containing compounds can be directly initiated by O₂ as the ideal green oxidant to generate sulfur-centered radicals, and the corresponding radical reactions provide a novel approach to the construction of S—S, P—S and C—S bonds. These reactions can be performed under mild conditions without the use of toxic reagents, transition metals and strong oxidants. In this review, the recent progress in the construction of S—S, P—S and C—S bonds involving O₂-initiated sulfur-centered radicals is introduced on the basis of different reaction types.

Key words: oxygen, sulfur-centered radicals, organosulfur compounds, radical reactions

引用此文

赵喜, 区颖聪, 刘艳, Keiji Maruoka, 陈迁. 氧气引发的硫中心自由基参与的构建S—S、P—S和C—S键研究进展[J]. 有机化学, 2021, 41(9): 3366-3378.

Xi Zhao, Yingcong Ou, Yan Liu, Keiji Maruoka, Qian Chen. Recent Progress in the Construction of S—S, P—S and C—S Bonds Involving O₂-Initiated Sulfur-Centered Radicals[J]. Chinese Journal of Organic Chemistry, 2021, 41(9): 3366-3378.

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图/表 37

图式1. 氧气引发的硫自由基反应

Scheme 1. Reactions of O2-initiated thiyl radicals

图式2. 超声辅助的空气氧化硫酚(醇)反应

Scheme 2. Air oxidation of thiols under sonication

图式3. 生物基绿色溶剂介导的二硫化物合成方法

Scheme 3. Bio-based green solvent mediated disulfide synthesis

图式4. 空气氛围下碱催化硫酚(醇)的交叉脱氢偶联反应

Scheme 4. Base-catalyzed cross-dehydrogenative coupling of thiols under air

图式5. Cs2CO3催化的氧气氧化P(O)H化合物和硫酚(醇)的交叉脱氢偶联反应

Scheme 5. Cs2CO3-catalyzed aerobic oxidative cross-dehydro- genative coupling of P(O)H compounds with thiols

图式6. K2CO3促进的空气氧化亚磷酸三烷基酯和硫酚的交叉偶联反应

Scheme 6. K2CO3-promoted aerobic oxidative cross-coupling of trialkyl phosphites with thiophenols

图式7. 氧气氛围下离子液体催化的烯烃双官能团化反应

Scheme 7. Ionic liquid-catalyzed difunctionalization of alkenes under oxygen

图式8. β-羟基硫醚和β-羟基亚砜的可控合成

Scheme 8. Controlled synthesis of β-hydroxy sulfides and β- hydroxy sulfoxides

图式9. 空气氛围下烯烃的双官能团化反应

Scheme 9. Difunctionalization of alkenes under air

图式10. 氧气氛围下烯烃的双官能团化反应

Scheme 10. Difunctionalization of alkenes under O2

图式11. 空气氛围下卤代烯烃和硫酚反应直接合成β-羰基硫醚

Scheme 11. Direct synthesis of β-keto sulfides via reactions of alkenyl halides with thiophenols under air

图式12. 氧气氛围下烯基磷酸酯和硫酚反应直接合成β-羰基硫醚

Scheme 12. Direct synthesis of β-keto sulfides via reactions of vinyl phosphates with thiophenols under O2

图式13. 空气氛围下2-氨基苯硫酚和α,β-不饱和酮的环合反应

Scheme 13. Cyclization of 2-aminobenzenethiols with α,β-unsaturated ketones under air

图式14. 空气引发的烯烃双硫醚化反应

Scheme 14. Air-induced bis-sulfenylation of alkenes

图式15. 空气氛围下可见光引发的芳基重氮砜与硫酚(醇)的氧化偶联反应

Scheme 15. Visible-light-initiated oxidative coupling of aryldiazo sulfones with thiols under air

图式16. 噻唑鎓盐催化的烯烃和炔烃的硫氢化反应

Scheme 16. Hydrothiolation of alkenes and alkynes catalyzed by thiazolium salts

图式17. 空气氛围下烯烃的硫氢化及双官能团化反应

Scheme 17. Hydrothiolation and difunctionalization of alkenes under air

图式18. 氧气引发的硫酚与炔烃的环合反应

Scheme 18. Oxygen-triggered cyclization of thiophenols and alkynes

图式19. 炔酸芳基酯的硫自由基串联反应

Scheme 19. Thiyl radical cascade reaction of aryl alkynoates

图式20. 空气氛围下烯烃和芳基亚磺酸反应直接合成β-羟基砜

Scheme 20. Direct synthesis of β-hydroxysulfones via reactions of alkenes with arylsulfinic acids under air

图式21. 空气氛围下末端炔烃的双官能团化反应

Scheme 21. Difunctionalization of terminal alkynes under air

图式22. 空气氛围下烯烃和芳基亚磺酸反应直接合成β-羰基砜

Scheme 22. Direct synthesis of β-keto sulfones via reactions of alkenes with arylsulfinic acids under air

图式23. 氧气氛围下烯基磷酸酯和芳基亚磺酸反应直接合成β-羰基砜

Scheme 23. Direct synthesis of β-keto sulfones via reactions of vinyl phosphates with arylsulfinic acids under O2

图式24. 空气氛围下铁催化的烯烃双官能团化

Scheme 24. Iron-catalyzed difunctionalization of alkenes under air

图式25. 空气氛围下芳基亚磺酸和NBS参与的烯烃双官能团化

Scheme 25. Difunctionalization of alkenes with arylsulfinic acids and NBS under air

图式26. 氧气氛围下磺酰肼参与的烯烃双官能团化

Scheme 26. Difunctionalization of alkenes with sulfonyl hydrazides under O2

图式27. 空气氛围下铜催化的烯烃与硫酚(醇)的氧化偶联反应

Scheme 27. Cu-catalyzed oxidative coupling of alkenes with thiols under air

图式28. 氧气引发的芳基乙烯的硫氰化反应

Scheme 28. O2-induced thiocyanation of styrenes

图式29. 环己酮和2-氨基苯硫酚之间的环合反应

Scheme 29. Cyclization of cyclohexanones and 2-aminobenzenethiols

图式30. 空气氛围下吡唑啉酮的C(sp3)—H键硫醚化反应

Scheme 30. Sulfenylation of C(sp3)—H bonds of pyrazolones under air

图式31. 空气氛围下2-氨基苯硫酚和酮之间的自由基环合

Scheme 31. Radical cyclization of 2?aminobenzenethiols and ketones under air

图式32. 空气氛围下1,3-二羰基化合物的C(sp3)—H键硫醚化反应

Scheme 32. Sulfenylation of C(sp3)—H bonds of 1,3-dicarbonyl compounds under air

图式33. 氧气氛围下3-氧代丁酰胺或丁酸酯的硫醚化/C—C键裂解反应

Scheme 33. Sulfenylation and C—C bond cleavage of 3-oxobutyric amides/esters under O2

图式34. 氧气氛围下3-氧代丁酰胺的α-双硫醚化/C—C键裂解反应

Scheme 34. α-Disulfenylation and C—C bond cleavage of 3- oxobutyric amides under O2

图式35. 空气氛围下亚甲基插入S—S键反应

Scheme 35. Methylene insertion into disulfide bonds under air

图式36. 空气氛围下铁催化的羰基α-硫醚化反应

Scheme 36. Iron-catalyzed α-sulfenylation of ketones under air

图式37. 空气氛围下氧杂蒽衍生物的C(sp3)—H键直接硫醚化反应

Scheme 37. Direct C(sp3)—H sulfenylation of xanthene derivatives under air

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