Applied Organometallic Chemistry, Год журнала: 2022, Номер 36(11)
Опубликована: Авг. 16, 2022
An efficient and selective insertion of indoles into ethynylethylene carbonates has been achieved via Cp X Co(III)‐catalyzed C–H functionalization. Compared with a Cp*Co(III) catalyst, the more sterically hindered Co(III) improved selectivity rare 1,2‐insertion. This protocol provides an approach for synthesizing various vinylindoles in good yields high regioselectivity.
Язык: Английский
Angewandte Chemie, Год журнала: 2023, Номер 135(47)
Опубликована: Окт. 16, 2023
Abstract Catalytic asymmetric transformations by dearomatization have developed into a widely applicable synthetic strategy, but heavily relied on the use of arenes bearing heteroatom. In this case, is facilitated involvement p ‐orbital electron Different from conventional substrate‐dependent model, here we demonstrate that activation d transition‐metal center can serve as driving force for dearomatization, and applied to development novel alkynyl copper remote substitution reaction. A newly modified PyBox chiral ligand enables construction valuable diarylmethyl triarylmethyl skeletons in high enantioselectivities. An unexpected tandem process involving sequential substitution/cyclization/1,5‐H shift leads formation enantioenriched C−N axis. gram‐scale reaction various downstream highlight robustness method potential products. Preliminary mechanistic studies reveal mononuclear Cu‐catalyzed process.
Язык: Английский
Процитировано
2
Advanced Synthesis & Catalysis, Год журнала: 2021, Номер 364(3), С. 565 - 573
Опубликована: Окт. 29, 2021
Abstract Rh(I)‐catalyzed decarboxylative arylation of alkynyl cyclic carbonates using commercially available and low‐toxic aryl boronic acids has been disclosed. Depending on the nature carbonates, methodology provides a straightforward platform to access either substituted 2,3‐allenols or 1,3‐butadiene derivatives. Internal undergo monoarylation conveniently afford with high syn ‐selectivity for hydroxy groups. Whereas, terminal led formation diarylated derivatives having cis ‐configuration two groups via allenyl rhodium(I)alkoxide intermediate. The compatibility various functional allowed develop library diversely functionalized scaffolds excellent regioselectivity in good yields. Late‐stage transformation series natural products highlights wide applicability process. Additionally, scale‐up experiments downstream transformations α ‐allenol into other valuable heterocycles illustrate efficacy protocol. magnified image
Язык: Английский
Процитировано
4
Angewandte Chemie, Год журнала: 2023, Номер 135(14)
Опубликована: Фев. 10, 2023
Abstract Transition‐metal‐catalysed reactions of cyclic ethynylethylene carbonates have been intensively studied because their robustness in new bond formation and diversified molecule construction. Known reaction modes usually involve a substitution step occurring at either the propargylic or terminal alkyne positions. Here, we report an unprecedented pattern which first undergo rearrangement to release allenal intermediates, subsequently react with diverse nucleophiles furnish synthetically useful allylic allenols, phosphorus ylides, cyclopropylidene ketones through addition process rather than pathway. The products enable various further transformations, mechanistic studies theoretical calculations reveal that does not proceed via semipinacol type [1,2]‐hydride shift, but base‐mediated deprotonation as key induce rearrangement.
Язык: Английский
Процитировано
1
European Journal of Organic Chemistry, Год журнала: 2024, Номер 27(25)
Опубликована: Апрель 9, 2024
Abstract A formal [4+2] cycloaddition reaction of ethynylethylene carbonates and 2‐aminophenols has been developed for the synthesis 3,4‐dihydro‐2 H ‐benzo[ b ][1,4]oxazines bearing quaternary carbon atoms. The features mild conditions, good functional group compatibility yields. Furthermore, when using chiral PyBox ligand, this strategy could also achieve asymmetric ][1,4]oxazines. Application studies indicated that hydroxymethyl final products was an excellent can be further modified easily.
Язык: Английский
Процитировано
0
Applied Organometallic Chemistry, Год журнала: 2022, Номер 36(11)
Опубликована: Авг. 16, 2022
An efficient and selective insertion of indoles into ethynylethylene carbonates has been achieved via Cp X Co(III)‐catalyzed C–H functionalization. Compared with a Cp*Co(III) catalyst, the more sterically hindered Co(III) improved selectivity rare 1,2‐insertion. This protocol provides an approach for synthesizing various vinylindoles in good yields high regioselectivity.
Язык: Английский
Процитировано
2