过渡金属催化有机硫化物C-S断裂反应的研究进展

doi:10.12422/j.issn.1006-396X.2023.01.007

摘要/Abstract

摘要：

有机硫化物广泛存在于石油、煤炭等自然资源中，具有丰富的资源储备。在石油炼制工业中，通常需要通过C-S断裂进行石油馏分的脱硫。其中，过渡金属催化的C-S断裂反应因具有效率高、条件温和、污染小等优点而备受研究者的关注。总结了过渡金属催化不同类型有机硫化物C-S断裂反应的最新进展，对Pd、Cu、Ni、Fe等催化体系的反应机理提出了见解，并对该类反应的发展前景进行了展望。

关键词: 交叉偶联反应, 过渡金属催化, C-S, 有机硫化物, 研究进展

Abstract:

Organic sulfides widely exist in natural resources such as petroleum and coal,which have abundant resource reserves.In the petroleum refining industry,the cleavage of C-S bonds is usually required for the desulfurization of petroleum fractions. Among them,the transition metal?catalyzed cleavage reactions of C-S bonds have attracted the attention of researchers owing to the advantages of high efficiency,mild conditions,and low pollution.This review summarizes the progress in transition metal?catalyzed C-S bond cleavage reactions of different types of organic sulfides,and provides insights into Pd,Cu,Ni and Fe catalytic systems and mechanisms.Moreover,the development of such reactions is proposed.

Key words: Cross?coupling reaction, Transition metal catalysis, C-S bond, Organic sulfides, Research progress

中图分类号:

TQ31.2

田帅男, 孙然, 李蕾, 王贺. 过渡金属催化有机硫化物C-S断裂反应的研究进展[J]. 石油化工高等学校学报, 2023, 36(1): 48-57.

Shuainan Tian, Ran Sun, Lei Li, He Wang. Research Progress in Transition Metal⁃Catalyzed C-S Bond Cleavage of Organic Sulfides[J]. Journal of Petrochemical Universities, 2023, 36(1): 48-57.

图/表 21

图1 “Liebeskind?Srogl”交叉偶联反应

Fig.1 “Liebeskind–Srogl” cross?coupling reaction

图2 CuI/Ag2CO3催化的硫代酸酯的C-S断裂反应

Fig.2 CuI/Ag2CO3?catalyzed C-S bond cleavage of thiolesters

图3 Ni催化的硫代酸酯的脱羰硫醚化反应

Fig.3 Nickel?catalyzed decarbonylative thioetherification of thioesters

图4 双(1,5?环辛二烯)Ni催化的α?羰基硫代酸酯的脱羰基化反应

Fig.4 Ni(COD)2 catalyzed decarbonylation of α?ketothioesters

图5 醋酸钯催化的硫代酸酯的分子内脱羰偶联反应

Fig.5 Pd(OAc)2 catalyzed intramolecular decarbonylation coupling of thioesters

图6 Pd催化烷硫基取代的吲哚和呋喃衍生物的C-S断裂反应

Fig.6 Pd?catalyzed C-S bond cleavage of thioalkylindoles and thioalkylfurans

图7 α?羰基二硫缩烯酮的C-S断裂反应

Fig.7 C-S bond cleavage of α-oxoketene dithioacetal

图8 Rh催化的芳基硫醚C-S断裂反应

Fig.8 Rh catalyzed C-S bond cleavage of alkylthioarenes

图9 Cu催化的α?羰基二硫缩烯酮与重氮化合物的环化反应

Fig.9 Cu?catalyzed cyclization of the α-oxoketene dithioacetal with diazo compounds

图10 Ni催化的芳基硫醚的氰化反应

Fig.10 Ni?catalyzed cyanation of aryl sulfide

图11 Fe催化的芳基锌试剂和2?吡啶基二氟甲基砜的二氟甲基化反应

Fig.11 Iron?catalyzed difluoromethylation of arylzinc reagents with difluoromethyl 2-pyridyl sulfone

图12 Ni催化的苯基四氮唑砜与芳基锌试剂C(sp3)?C(sp2)的偶联反应

Fig.12 Nickel?catalyzed C(sp3)?C(sp2) coupling between PT?sulfones and aryl zinc reagents

图13 二芳基甲基砜的脱硫胺化反应

Fig.13 Desulfonylative amination of benzhydryl sulfones

图14 Pd?NHC催化的二芳基亚砜和硼酸的交叉偶联反应

Fig.14 Pd-NHC catalyzed cross-coupling reaction of diphenyl sulfoxide and boronic acid

图15 Ni催化的二芳基亚砜的硼化反应

Fig.15 Ni?catalyzed borylation of diaryl sulfoxides

图16 芳基亚磺酸钠与芳基卤化物的交叉偶联反应

Fig.16 Cross?coupling of aryl sulfinates with aryl halides

图17 吡啶基亚磺酸钠与芳基卤化物的交叉偶联反应

Fig.17 Cross?coupling of sodium pyridyl sulfinate with arylhalides

图18 吡啶酮与芳基磺酰氯的脱硫反应

Fig.18 Desulfurization reaction of pyridone and arylsulfonyl chloride

图19 芳基硫氰酸酯中的C-S断裂

Fig.19 C-S bond cleavage in aryl thiocyanates

图20 硫脲和芳基卤化物的偶联反应

Fig.20 Direct coupling of thioureas and aryl halides

图21 芳基锍鎓盐与芳基卤化物的偶联反应

Fig.21 Direct coupling of aryl sulfonium salts and aryl halides

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