From Radical Coupling to Enantioselective Controlled Protonation: Advancing Precise Construction of Stereocenters DOI
Xin Sun, Wenjie Zhu, Yanli Yin

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 23, 2025

Recent advancements in green and sustainable platforms, particularly visible light-driven photocatalysis, have spurred significant progress radical chemistry, enabling the efficient synthesis of important molecules from simple readily available feedstocks under mild conditions. However, rapid orbital flipping high reactivity radicals pose substantial challenges for achieving precise enantiocontrol stereocenter formation via coupling. In this study, we present a generic strategy that modulates elusive approach, facilitating enantiocontrollable protonation through 1,3-boron migration. We successfully developed two previously photocatalytic asymmetric transformations: de Mayo reaction utilizing energy transfer three-component reactions cyanoazaarenes initiated by single-electron transfer. Moreover, incorporation cost-effective D2O as deuterium source enhances synthetic pharmaceutical significance method, offering valuable tool future applications.

Язык: Английский

Enantioselective Catalytic Hantzsch Dihydropyridine Synthesis DOI
Xinyue Hu, Long Chen, Hongye Li

и другие.

ACS Catalysis, Год журнала: 2023, Номер 13(10), С. 6675 - 6682

Опубликована: Май 1, 2023

Optically enriched Hantzsch dihydropyridines bearing different ester groups were obtained through the asymmetric catalytic cascade reaction between 3-amino-2-butenoates and (Z)-2-arylidene-3-oxobutanoates. The N,N′-dioxide/NiII or NdIII complex catalysts disclosed to be efficient, furnishing a variety of products, including drugs like nitrendipine, nimodipine, felodipine, in high yields (up 99% yield) with excellent enantioselectivities ee). Two enantiomers products can readily via exchange group two reactants. In addition, axial chiral 4-arylpyridines also afforded an oxidation process.

Язык: Английский

Процитировано

15
Chiral Lewis Acid-Catalyzed Asymmetric Multicomponent Michael Reaction through [1,2]-Phospha-Brook Rearrangement DOI
Qianchi Lin, Siyuan Wang,

Rui Weng

и другие.

Organic Letters, Год журнала: 2023, Номер 25(34), С. 6262 - 6266

Опубликована: Авг. 21, 2023

The multicomponent catalytic asymmetric Pudovik addition/[1,2]-phospha-Brook rearrangement/Michael reaction sequence of isatins, phosphites, and 4-oxobutenoates was realized. A series oxindole derivatives containing two contiguous stereocenters obtained in high yields excellent stereoselectivities (up to >99% yield, >95:5 dr, ee) using a chiral Lewis acid catalyst. possible model is presented illustrate the stereocontrol.

Язык: Английский

Процитировано

14
Asymmetric Photoenolization/Diels–Alder Reaction of 2-Methylbenzaldehydes and 2-Alkylbenzophenones with Chromones DOI
Yuhao Mo, Lichao Ning,

Luo Zhe

и другие.

ACS Catalysis, Год журнала: 2024, Номер 14(9), С. 6687 - 6695

Опубликована: Апрель 16, 2024

The asymmetric photoenolization/Diels–Alder reaction provides a straightforward and atom-economical route to complex chiral polycyclic rings. In comparison with well-developed transformations of 2-alkylbenzophenones, the enantioselective 2-methylbenzaldehydes was challenging due shorter-lived unstable photoenol intermediates. Herein, we present highly chromones. Chiral N,N′-dioxide/ScIII YbIII complexes were found interact both intermediates chromones simultaneously, accelerating Diels–Alder in an efficient stereoselective manner. Experimental studies DFT calculations carried out understand mechanism origin stereoselectivity. addition, 2-alkylbenzophenones suitable substrates. A series fused rings vicinal multisubstituted stereocenters afforded good yields high diastereo- enantioselectivities.

Язык: Английский

Процитировано

6
Metal-free photoinduced C(sp3)–H/C(sp3)–H cross-coupling to access α‑tertiary amino acid derivatives DOI Creative Commons
Yujun Li, Shaopeng Guo, Qinghan Li

и другие.

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Окт. 6, 2023

The cross-dehydrogenative coupling (CDC) reaction is the most direct and efficient method for constructing α-tertiary amino acids (ATAAs), which avoids pre-activation of C(sp3)-H substrates. However, use transition metals harsh conditions are still significant challenges these reactions that urgently require solutions. This paper presents a mild, metal-free CDC construction ATAAs, compatible with various benzyl C-H substrates, functionalized alkyl good regioselectivity. Notably, our exhibits excellent functional group tolerance late-stage applicability. According to mechanistic studies, one-step synthesized bench-stable N-alkoxyphtalimide generates highly electrophilic trifluoro ethoxy radical serves as key intermediate in process acts hydrogen atom transfer reagent. Therefore, additive-free offers promising strategy synthesis ATAAs under mild conditions.

Язык: Английский

Процитировано

13
Applications of Organosilanes in Visible Light‐induced Catalytic Asymmetric Reactions DOI
Liuzhen Hou, Weidi Cao, Xiaoming Feng

и другие.

ChemCatChem, Год журнала: 2024, Номер unknown

Опубликована: Март 27, 2024

Abstract Over the past decades, visible light‐mediated photocatalysis has found a mainstream of applications in synthetic chemistry. Organosilanes have been proven to be useful class electron donors generate highly active radical species via photoinduced single transfer oxidation/fragmentation sequence, which may undergo follow‐up coupling or addition process. This minireview highlights comprehensive advances organosilanes photoredox catalyzed asymmetric organic synthesis, with particular emphasis placed on reaction mechanisms. We hope that this review will inspire further design and development new reactions such readily accessible reagents.

Язык: Английский

Процитировано

5
Visible-light-driven asymmetric aldol reaction of ketones and glycinates via synergistic Lewis acid/photoredox catalysis DOI Creative Commons
Jiuqi Tan, Longqing Yang,

Hanyu Su

и другие.

Chemical Science, Год журнала: 2024, Номер 15(39), С. 16050 - 16058

Опубликована: Янв. 1, 2024

We have synthesized β-diaryl-β-hydroxyl-α-amino acid derivatives through radical addition-type aldol reaction, which was confirmed by spectroscopic experiments, control and DFT calculations.

Язык: Английский

Процитировано

5
Recent advances in the asymmetric catalytic construction of oxa-quaternary carbon centers DOI

Yu‐Ping He,

Di Tian,

Xingzi Li

и другие.

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(12), С. 3110 - 3129

Опубликована: Янв. 1, 2023

This review focuses on the very recent advances (from 2020 to beginning of 2023) in enantioselective catalytic reactions for construction oxa-quaternary stereocenters.

Язык: Английский

Процитировано

11
Catalytic Asymmetric Synthesis of Axially and Centrally Chiral 1,2-Dihydrobenzofuro[3,2-b]pyridines through a [2 + 2] Cycloaddition/Retroelectrocyclization/Re-Cycloaddition Cascade DOI
Wanlong Xiao,

Fang Li,

Xiaohua Liu

и другие.

Organic Letters, Год журнала: 2023, Номер 25(44), С. 8005 - 8009

Опубликована: Окт. 31, 2023

A catalytic asymmetric tandem cyclization of azadienes and ortho-alkynylnaphthols accelerated by the chiral N,N′-dioxide-gadolinium(III) complex is disclosed. This method allows synthesis a range 1,2-dihydrobenzofuro[3,2-b]pyridines containing both axially centrally elements in high yields excellent stereoselectivities (up to >99% yield, 91:9 dr, 98% ee). control experiment revealed that this process proceeded through multistep [2 + 2] cycloaddition/retroelectrocyclization/tautomerism/1,6-conjugate addition cascade.

Язык: Английский

Процитировано

11
Visible-light-induced chemo-, diastereo- and enantioselective α-C(sp3)−H functionalization of alkyl silanes DOI Creative Commons
Lili Feng, Xiaofan Chen, Ning Guo

и другие.

Chemical Science, Год журнала: 2023, Номер 14(17), С. 4516 - 4522

Опубликована: Янв. 1, 2023

A visible-light-induced chemo-, diastereo- and enantioselective α-C(sp 3 )–H functionalization of alkyl silanes with benzosultams was realized under a bimetallic synergetic catalysis.

Язык: Английский

Процитировано

10
Photoredox-catalyzed C( sp 3 )─H radical functionalization to enable asymmetric synthesis of α-chiral alkyl phosphine DOI Creative Commons
Zhenda Tan, Yangbin Liu, Xiaoming Feng

и другие.

Science Advances, Год журнала: 2024, Номер 10(23)

Опубликована: Июнь 5, 2024

α-Chiral alkyl phosphines are privileged structural motifs with a wide application in organic and medical synthesis. It is highly desirable to develop stereoselective methods prepare these enantioenriched molecules. The incorporation of C( sp 3 )─H functionalization chiral phosphine chemistry much less explored, probably because the weak reactivity bonds and/or challenging site- stereoselectivity issues. Herein, we disclose synergistic catalysis system enable an enantioselective radical addition process α-substituted vinylphosphine oxides. An array diverse α-chiral phosphors compounds smoothly accessed by using readily available chemicals as inert bond reagent, such sulfides, amines, alkenes, toluene derivatives, exerting remarkable chemo-, site-, enantioselectivity. On basis mechanistic studies, both activation stereochemistry-determining step proposed involve single-electron transfer/proton transfer process.

Язык: Английский

Процитировано

4