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

Heyin Li,

Mengjun Huang,

Zhenlei Zou

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(47), P. 13893 - 13901

Published: Jan. 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.

Language: Английский

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

Jinhui Xie

et al.

Nature Synthesis, Journal Year: 2023, Volume and Issue: 2(2), P. 140 - 151

Published: Jan. 5, 2023

Language: Английский

Citations

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

Xingxing Ma,

Mengwei Tan,

Luo Li

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(1), P. 42 - 53

Published: Jan. 1, 2024

Language: Английский

Citations

30
Ligand relay catalysis for cobalt-catalyzed sequential hydrosilylation and hydrohydrazidation of terminal alkynes DOI Creative Commons
Yufeng Sun, Jun Guo,

Xuzhong Shen

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Feb. 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.

Language: Английский

Citations

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

Arti Ramani,

Bhargav Desai,

Monak Patel

et al.

Asian Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 11(5)

Published: March 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.

Language: Английский

Citations

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

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(6), P. 1654 - 1687

Published: May 4, 2023

Language: Английский

Citations

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

Xin‐Rui Mao,

Shuo Song

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(11)

Published: Jan. 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.

Language: Английский

Citations

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

Sheng‐Wen Xu,

Hongjian Zhang, Jingkai Xu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7791 - 7802

Published: March 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).

Language: Английский

Citations

15
Stereospecific Assembly of Trisubstituted Alkenes via Photoinduced Nitrogen‐Centered Radical‐Triggered C—C Bond Cleavage/Functionalization of Oxime Esters DOI

Yu Bao,

Zhi‐Jie Song,

Jin‐Long Dai

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(12), P. 1399 - 1406

Published: Feb. 29, 2024

Comprehensive Summary A general and convenient photoredox‐catalyzed acylation alkylcyanation of MBH acetates has been established, enabling the assembly C(sp 2 )–C(sp 3 ) bond by a nitrogen‐centered radical strategy for synthesis trisubstituted alkenes in moderate to excellent chemical yields (48 examples total). The reaction with acyl (indanone) oxime esters afforded containing 1,4‐dicarbonyl groups. Interestingly, use Eosin Y as photocatalyst catalytic system resulted formation distal cyano group‐anchored via deconstructive functionalization cycloketone esters. Notably, these resulting compounds could be applied late‐stage transformations, providing important methods dihydropyridazin‐3(2 H )‐one.

Language: Английский

Citations

10
Copper- and Palladium-Cocatalyzed Chemo-, Regio-, Stereo-, and Atroposelective Arylboration of 1,3-Enynes DOI
Wangyang Li, Haohua Chen,

Yanping Zheng

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(15), P. 11318 - 11331

Published: July 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.

Language: Английский

Citations

10
Cobalt-catalyzed alkyne hydrosilylation as a new frontier to selectively access silyl-hydrocarbons DOI
Jung‐Woo Park

Chemical Communications, Journal Year: 2021, Volume and Issue: 58(4), P. 491 - 504

Published: Nov. 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.

Language: Английский

Citations

43