Transition-metal free thiocyanooxygenation of functionalized alkenes: facile routes to SCN-containing dihydrofurans and lactones

Guo, Li‐Na; Gu, Yu-Rui; Ye, Hua; Hu, Jie

doi:10.1039/c6ob00221h

Cited by 55 publications

(13 citation statements)

References 71 publications

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“…Compounds 3a,b 46) 3c, 47) 3d, 48) and, 8a-d 49) were prepared according to the literatures and identified with 1 H-NMR by comparison with the reported ones.…”

Section: Methodsmentioning

confidence: 99%

Development of Nitrolactonization Mediated by Iron(III) Nitrate Nonahydrate

Yoshimura

Umeda

Takahashi

et al. 2020

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…Compounds 3a,b 46) 3c, 47) 3d, 48) and, 8a-d 49) were prepared according to the literatures and identified with 1 H-NMR by comparison with the reported ones.…”

Section: Methodsmentioning

confidence: 99%

Development of Nitrolactonization Mediated by Iron(III) Nitrate Nonahydrate

Yoshimura

Umeda

Takahashi

et al. 2020

CHEMICAL & PHARMACEUTICAL BULLETIN

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“…For instance, as shown in Scheme 1, the first route involved ortho ‐alkyl benzoic acids followed by oxidation of the alkyl chain and ring closing (Scheme 1A [14] ). [15–17] The second was a copper‐catalyzed cyclization of ortho ‐bromo‐benzylalcohols (Scheme 1B) [18] . The third methodology (Scheme 1C) can be classified as a convergent synthetic route as a part of the hydrocarbon chain (R 2 ) of the product comes from a second reagent.…”

Section: Introductionmentioning

confidence: 99%

Critical Ligand and Salt Effects in Organomagnesiate‐Promoted 3,3‐Disubstituted Phthalides Synthesis from 2‐Iodobenzoate Derivatives

2021

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Phthalides, also called isobenzofuranones, are widespread in many biologically active compounds and natural products. To date, most of their synthetic routes are non‐convergent. Herein we report a convergent route using a metal halogen exchange (MHE) strategy. Indeed MHE of easily available 2‐iodobenzoate derivatives, using the bimetallic organomagnesiate complex (rac)‐(BIPHEN)BuMgLi, where (rac)‐BIPHEN is (rac)‐5,5′,6,6′‐tetramethyl‐3,3′‐di‐t‐butyl‐1,1′‐biphenyl‐2,2′‐diol, followed by addition of a ketone which lead to an intramolecular cyclisation, and the formation of a series of diverse 3,3‐disubstituted isobenzofuranones in good yield. Among the several MHE agents investigated, (rac)‐(BIPHEN)BuMgLi was the only one to make such a process possible with full tolerance of various reactive functional substituents useful for subsequent transformations. The synthetic pathway to access the magnesiate has been found to play a prominent role in its reactivity. Therefore, the bimetallic magnesiate complex has been characterized by solution‐state 1H, 7Li and 1H DOSY NMR experiments.

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“…In contrast, the 1,2-difunctionalization of alkenes comprising a cascade thiocyanation and β-functionalization is more appealing from a synthetic perspective because of its high economy of steps and atoms. In recent years, many metal-free and transition-metal-catalyzed transformations such as thiocyanooxygenation [ 24 , 25 , 26 , 27 ], dithiocyanation [ 28 , 29 ], thiocyanophosphinoylation [ 30 ], thiotrifluoromethylation [ 31 ], and thiocyanoamination [ 32 ] have been developed ( Scheme 1 ). In spite of these significant advances, arylthiocyanation of alkenes via 1,2-difunctionalization remains relatively unexplored.…”

Section: Introductionmentioning

confidence: 99%

Ag/Pyridine Co-Mediated Oxidative Arylthiocyanation of Activated Alkenes

Kong

Chu

et al. 2018

Molecules

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An efficient Ag/pyridine co-mediated oxidative arylthiocyanation of activated alkenes via radical addition/cyclization cascade process was developed. This reaction could be carried out under mild conditions to provide biologically interesting 3-alkylthiocyanato-2-oxindoles in good to excellent yields. Mechanistic studies suggested a unique NCS• radical addition path and clarified the dual roles of catalytic pyridine as base and crucial ligand to accelerate the oxidation of Ag(I) to Ag(II), which is likely oxidant responsible for the formation of NCS• radical. These mechanistic results may impact the design and refinement of other radical based reactions proceeding through catalytic oxidations mediated by Ag(I)-pyridine/persulfate. The chemical versatility of thiocyanate moiety was also highlighted via SCN-tailoring chemistry in post-synthetic transformation for new S-C(sp3/sp2/sp), S-P, and S-S bonds constructions. The protocol provides an easy access to many important bioisosteres in medicinal chemistry and an array of sulfur-containing 2-oxindoles that are difficult to prepare by other approaches.

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Transition-metal free thiocyanooxygenation of functionalized alkenes: facile routes to SCN-containing dihydrofurans and lactones

Cited by 55 publications

References 71 publications

Development of Nitrolactonization Mediated by Iron(III) Nitrate Nonahydrate

Development of Nitrolactonization Mediated by Iron(III) Nitrate Nonahydrate

Critical Ligand and Salt Effects in Organomagnesiate‐Promoted 3,3‐Disubstituted Phthalides Synthesis from 2‐Iodobenzoate Derivatives

Ag/Pyridine Co-Mediated Oxidative Arylthiocyanation of Activated Alkenes

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