Palladium‐Catalyzed Insertion of Isocyanides into the C−S Bonds of Heteroaryl Sulfides

Otsuka, Shinya; Nogi, Keisuke; Yorimitsu, Hideki

doi:10.1002/ange.201802369

Cited by 9 publications

(4 citation statements)

References 89 publications

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“…1 13 C NMR data to previous reports. 99 tert-Butyl 2-(Benzo[d]thiazol-2-ylthio)ethylcarbamate (5j). A general procedure (GP1) was followed by using 2-chlorobenzothiazole (2 mmol, 1 equiv) and tert-butyl (2-mercaptoethyl)carbamate (2.4 mmol, 1.2 equiv) to obtain the desired product (527 mg, 85%) as a white solid.…”

Section: -(Dodecylthio)benzo[d]thiazole (5i)mentioning

confidence: 99%

Pd/PTABS: Low-Temperature Thioetherification of Chloro(hetero)arenes

et al. 2019

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The thioetherification of heteroaryl chlorides is an essential synthetic methodology that provides access to bioactive drugs and agrochemicals. Due to their (actual or potential) industrial importance, the development of efficient and lowtemperature protocols for accessing these compounds is a requirement for economic and ecologic reasons. A particular highly effective catalytic protocol using the Pd/ PTABS system at only 50 °C was developed accordingly. The coupling between chloroheteroarenes and a variety of less reactive arylthiols and alkylthiols was carried out with a high efficiency. Heteroarenes of commercial relevance such as purines and pyrimidines were also found to be useful substrates for the reported transformation. The commercial drug Imuran (azathioprine) was synthesized as an example, and its preparation could be optimized. DFT studies were performed to understand the electronic effects of the tested ligands on the catalytic reaction.

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Section: -(Dodecylthio)benzo[d]thiazole (5i)mentioning

confidence: 99%

Pd/PTABS: Low-Temperature Thioetherification of Chloro(hetero)arenes

et al. 2019

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“…Moderate yield was observed in a palladium-mediated isocyanide insertion, the product of which was isolated as 8 after acidic workup. 30 Fortunately, by treating 2a with ammonium molybdate tetrahydrate, the sulfone product 9 could be formed in quantitative yield with no apparent oxidation of the olefin. 31 Sulfone 9 can be subsequently modified through several methods.…”

Section: Scheme 3 Results With Tri-and Tetrasubstituted Olefins Amentioning

confidence: 99%

Synthetic and Mechanistic Studies of a Versatile Heteroaryl Thioether Directing Group for Pd(II) Catalysis

et al. 2019

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A weakly coordinating monodentate heteroaryl thioether directing group has been developed for use in Pd(II) catalysis to orchestrate key elementary steps in the catalytic cycle that require conformational flexibility in a manner that is difficult to accomplish with traditional strongly coordinating directing groups. This benzothiazole thioether, (BT)S, directing group can be used to promote oxidative Heck reactivity of internal alkenes, providing a wide range of products in moderate to high yields. To demonstrate the broad applicability of this directing group, an arene C–H olefination method was also successfully developed. Reaction progress kinetic analysis provides insights into the role of the directing group in each reaction, which is supplemented with computational data for the oxidative Heck reaction. Furthermore, this (BT)S directing group can be transformed into a number of synthetically useful functional groups, including a sulfone for Julia olefination, allowing it to serve as a “masked olefin” directing group in synthetic planning. In order to demonstrate this synthetic utility, natural products (+)-salvianolic acid A and salvianolic acid F are formally synthesized using the (BT)S-directed C–H olefination as the key step.

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“…14, 153.45, 141.13, 138.32, 135.35, 131.63, 131.22, 128.80, 128.32, 127.74, 127.70, 127.62, 126.20, 124.38, 121.64, 121.12, 32.70, 32.05, 31.42, 29.74, 29.72, 29.65, 29.52, 29.45, 27.60, 22.83, 19.98, 14. 94, 153.11, 147.05, 147.03, 139.34, 135.53, 134.61, 134.54, 131.41, 128.74, 126.38, 125.78, 124.74, 122.03, 121.18, 120.85, 120.67, 31.72, 20. 8): The title compound was prepared following a literature procedure. 11 To a 25-mL round-bottom flask equipped with a magnetic stir bar were added (E)-2-((4-phenylbut-3-en-1yl)thio)benzothiazole (2a) (0.500 mmol, 1 equiv), Pd(PPh3)4 (5 mol%), 1,1'-bis(diphenylphosphino)ferrocene (5 mol%), Zn(OAc)2 (0.125 mmol, 0.25 equiv), and K3PO4 (0.125 mmol, 0.25 equiv). The flask was sealed with a rubber septum and filled with N2.…”

Section: General Procedures For C−h Functionalizationmentioning

confidence: 99%

Synthetic and Mechanistic Studies of a Versatile Heteroaryl Thioether Directing Group for Pd(II) Catalysis

Romine¹,

Yang²,

Karunananda³

et al. 2019

Preprint

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A weakly coordinating monodentate heteroaryl thioether directing group has been developed for use in Pd(II) catalysis to orchestrate key elementary steps in the catalytic cycle that require conformational flexibility in a manner that is difficult to accomplish with traditional strongly coordinating directing groups. This benzothiazole thioether, (BT)S, directing group can be used to promote oxidative Heck reactivity of internal alkenes providing a wide range of products in moderate to high yields. To demonstrate the broad applicability of this directing group, arene C–H olefination was also successfully developed. Reaction progress kinetic analysis provides insights into the role of the directing group in each reaction, which is supplemented with computational data for the oxidative Heck reaction. Furthermore, this (BT)S directing group can be transformed into a number of synthetically useful functional groups, including a sulfone for Julia olefination, allowing it to serve as a “masked olefin” directing group in synthetic planning. In order to demonstrate this synthetic utility, natural products (+)-salvianolic acid A and salvianolic acid F are formally synthesized using the (BT)S directed C–H olefination as the key step.

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Palladium‐Catalyzed Insertion of Isocyanides into the C−S Bonds of Heteroaryl Sulfides

Cited by 9 publications

References 89 publications

Pd/PTABS: Low-Temperature Thioetherification of Chloro(hetero)arenes

Pd/PTABS: Low-Temperature Thioetherification of Chloro(hetero)arenes

Synthetic and Mechanistic Studies of a Versatile Heteroaryl Thioether Directing Group for Pd(II) Catalysis

Synthetic and Mechanistic Studies of a Versatile Heteroaryl Thioether Directing Group for Pd(II) Catalysis

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