Photoredox-catalyzed stereo- and regioselective vicinal fluorosulfonyl-borylation of unsaturated hydrocarbons DOI Creative Commons

Heyin Li,

Mengjun Huang,

Zhenlei Zou

и другие.

Chemical Science, Год журнала: 2023, Номер 14(47), С. 13893 - 13901

Опубликована: Янв. 1, 2023

There has been considerable research on sulfur(vi) fluoride exchange (SuFEx) chemistry, which is considered to be a next-generation click reaction, and relies the unique balance between reactivity stability inherent in high valent organosulfur. The synthetic versatility of bifunctional handles containing fluorosulfonyl group presents great value opportunity for drug discovery. However, direct photoredox-catalyzed fluorosulfonyl-borylation process remains unexplored challenging due its system incompatibility limited strategies. Herein, we developed sequential photocatalytic radical difunctionalization strategy highly efficient stereoselective synthesis vicinal borides (VFSBs) with an integrated redox-active SO2F reagent. VFSBs acted as orthogonal synthons, were subjected range convenient transformations via cleavage C-B S(vi)-F bonds, including halogenation, Suzuki coupling, hydrogenation, SuFEX demonstrated potential VFSB moieties use skeleton linkage modification.

Язык: Английский

Synthesis of axially chiral alkenylboronates through combined copper- and palladium-catalysed atroposelective arylboration of alkynes DOI
Wangyang Li, Shanglin Chen,

Jinhui Xie

и другие.

Nature Synthesis, Год журнала: 2023, Номер 2(2), С. 140 - 151

Опубликована: Янв. 5, 2023

Язык: Английский

Процитировано

52
Ni-catalysed assembly of axially chiral alkenes from alkynyl tetracoordinate borons via 1,3-metallate shift DOI

Xingxing Ma,

Mengwei Tan,

Luo Li

и другие.

Nature Chemistry, Год журнала: 2024, Номер 16(1), С. 42 - 53

Опубликована: Янв. 1, 2024

Язык: Английский

Процитировано

28
Ligand relay catalysis for cobalt-catalyzed sequential hydrosilylation and hydrohydrazidation of terminal alkynes DOI Creative Commons
Yufeng Sun, Jun Guo,

Xuzhong Shen

и другие.

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Фев. 3, 2022

Sequential double hydrofunctionalizationalization of alkynes is a powerful method to construct useful vicinal compounds. Herein, we report cobalt-catalyzed sequential hydrosilylation/hydrohydrazidation afford 1,2-N,Si compounds via ligand relay catalysis. A phenomenon found that the tridentate anionic N-ligand (OPAQ) could capture cobalt ion from bidentate neutral P-ligand (Xantphos) complex. This protocol uses three abundant chemical feedstocks, alkynes, silanes, and diazo compounds, also features operationally simple, mild conditions, low catalyst loading (1 mol%), excellent functional group tolerance. The can be easily further derivatized various substituted silane derivatives Si-H functionalization, alcohols Fleming-Tamao oxidation, free amines amides N-N bond cleavage protection. asymmetric reaction carried out chiral products with up 86% ee. has been supported by control experiments absorption spectra.

Язык: Английский

Процитировано

46
Recent Advances in the Functionalization of Terminal and Internal Alkynes DOI

Arti Ramani,

Bhargav Desai,

Monak Patel

и другие.

Asian Journal of Organic Chemistry, Год журнала: 2022, Номер 11(5)

Опубликована: Март 9, 2022

Abstract Alkynes are one of the most fundamental and diverse functional groups utilized in organic synthesis. Over past few years, development efficient synthetic methodologies for functionalization alkynes has been an active area research. A plethora alkyne reactions have reported literature to construct functionalized alkene scaffolds, which important building blocks many natural products, pharmaceuticals, key intermediates various transformations. In this review, we describe recent advances with emphasis on substrate scope, limitations, regioselectivity control applications these reactions. This review covers from 2016 2021.

Язык: Английский

Процитировано

44
Catalytic asymmetric silicon-carbon bond-forming transformations based on Si-H functionalization DOI Open Access
Li Li, Wei‐Sheng Huang, Zheng Xu

и другие.

Science China Chemistry, Год журнала: 2023, Номер 66(6), С. 1654 - 1687

Опубликована: Май 4, 2023

Язык: Английский

Процитировано

38
Enantioselective Nickel‐Catalyzed Hydrosilylation of 1,1‐Disubstituted Allenes DOI
Tao Liu,

Xin‐Rui Mao,

Shuo Song

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(11)

Опубликована: Янв. 18, 2023

Here, we report the first example of Ni-catalyzed asymmetric hydrosilylation 1,1-disubstituted allenes with high level regioselectivities and enantioselectivities. The key to achieve this stereoselective reaction was development SPSiOL-derived bisphosphite ligands (SPSiPO). This protocol features broad substrate scope, excellent functional group, heterocycle tolerance, thus provides a versatile method for construction enantioenriched tertiary allylsilanes in straightforward atom-economic manner. DFT calculations were performed reveal mechanism origins enantioselectivity.

Язык: Английский

Процитировано

33
Photoinduced Selective B–H Activation of nido-Carboranes DOI

Sheng‐Wen Xu,

Hongjian Zhang, Jingkai Xu

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(11), С. 7791 - 7802

Опубликована: Март 10, 2024

The development of new synthetic methods for B–H bond activation has been an important research area in boron cluster chemistry, which may provide opportunities to broaden the application scope clusters. Herein, we present a reaction strategy direct site-selective functionalization nido-carboranes initiated by photoinduced cage via noncovalent cage···π interaction. As result, nido-carborane radical is generated through single electron transfer from 3D 2D photocatalyst upon irradiation with green light. resulting transient could be directly probed advanced time-resolved EPR technique. In air, subsequent transformations active have led efficient and selective B–N, B–S, B–Se couplings presence N-heterocycles, imines, thioethers, thioamides, selenium ethers. This protocol also facilitates both late-stage modification drugs synthesis nido-carborane-based drug candidates neutron capture therapy (BNCT).

Язык: Английский

Процитировано

15
Copper- and Palladium-Cocatalyzed Chemo-, Regio-, Stereo-, and Atroposelective Arylboration of 1,3-Enynes DOI
Wangyang Li, Haohua Chen,

Yanping Zheng

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(15), С. 11318 - 11331

Опубликована: Июль 15, 2024

Catalytic enantioselective borylation reactions of unsaturated bonds as powerful tools for the synthesis diverse chiral organoboron compounds have gained much attention and wide applications in various fields. However, atroposelective arylboration reaction with carbon–carbon triple 1,3-enynes to obtain axially 1,3-dienylboronates remains an elusive significant challenge. Hence, we develop a cooperative copper- palladium-catalyzed assemble plentiful function enriched single step from easily available 1,3-enynes, B2pin2, aryl bromides high levels chemo-, regio-, stereo-, atroposelectivity. The mild conditions lead good functional group tolerance, which is proven by broad substrate scope late-stage functionalizations bioactive or drug molecules. Moreover, can be scaled up, series further transformations achieved. It worth emphasizing that several olefin catalysts ligands axial chirality also synthesized through corresponding elaborations such products, explains transformative ability application potential 1,3-dienylboronates. mechanism experiment density theory (DFT) calculations revealed process copper palladium catalysis, indicating chemoselectivity regioselectivity boration are determined enyne insertion on copper, atroposelectivity controlled reductive elimination center. Meanwhile, calculation demonstrated distinct interactions between P═O C═O groups Pd Bpin center key transition state formation products varying configurations while employing identical configuration ligands.

Язык: Английский

Процитировано

10
Cobalt-Catalyzed Chemoselective and Divergent Synthesis of Vinylsilanes through Hydrosilylation of Acetylene DOI

Xianyang Long,

Dong Zhu, Shifa Zhu

и другие.

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4429 - 4440

Опубликована: Фев. 28, 2025

Язык: Английский

Процитировано

1
Cobalt-catalyzed alkyne hydrosilylation as a new frontier to selectively access silyl-hydrocarbons DOI
Jung‐Woo Park

Chemical Communications, Год журнала: 2021, Номер 58(4), С. 491 - 504

Опубликована: Ноя. 29, 2021

The hydrosilylation of alkynes is a chief chemical method for accessing range alkenylsilanes, which can be derivatized to obtain value-added hydrocarbons and utilized in diverse applications. While noble metal-based catalytic procedures have shown great success vinylsilanes within the context both academia industry, replacing metals with cheaper more abundant base has recently drawn significant interest due their sustainability competencies including unprecedented reactivity that could expand tools other types silicon-containing hydrocarbons. During past few years, number well-defined, robust cobalt-catalyst platforms broadly operate either Chalk-Harrod or modified mechanism emerged as new frontier field selective alkyne hydrosilylation. This review describes main features cobalt catalyst systems documented strong emphasis on ligand design reaction pathways involving Co-H and/or Co-silyl species-mediated elementary transformations achieve Markovnikov/anti-Markovnikov hydrosilylations well migratory transformations.

Язык: Английский

Процитировано

43