Photocatalyzed chemodivergent aerobic oxidation of naturally occurring Viridicatin and derivatives DOI Creative Commons
Yingxian Li, Hui Wang,

Xuemin Jia

et al.

Green Synthesis and Catalysis, Journal Year: 2024, Volume and Issue: unknown

Published: June 1, 2024

A chemodivergent reaction is an appealing way to construct molecules with enriched structure diversity in a controlled manner. plethora of methodologies were developed based on this concept, and transition metal-catalysis plays central role among others catalysis systems own its longstanding history. While organo-catalysis, especially photocatalysis, rather limited as these concepts only prevalent the last two decades. With ever-increasing importance such activation pathway would be meaningful direction. Herein, efficient strategy for visible light photocatalysis developed. By employing commercially available Rose Bengal photocatalyst, naturally occurring Viridicatin derivatives can transformed into three different types products through switchable single electron transfer (SET) or energy (EnT) processes. Mechanistic studies have revealed that oxygen reactive center, than carbon, favored, which accounts first example C-O homo-dimerization product.

Language: Английский

Enantioselective [2π + 2σ] Cycloadditions of Bicyclo[1.1.0]butanes with Vinylazaarenes through Asymmetric Photoredox Catalysis DOI

Qianqian Fu,

Shanshan Cao, Jiahao Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 8372 - 8380

Published: March 18, 2024

Here we present a highly enantioselective [2π + 2σ] photocycloaddition of bicyclo[1.1.0]butanes (BCBs). The reaction uses variety vinylazaarenes as partners and is catalyzed by polycyclic aromatic hydrocarbon (PAH)-containing chiral phosphoric acid bifunctional photosensitizer. A wide array pharmaceutically important bicyclo[2.1.1]hexane (BCH) derivatives have been synthesized with high yields, enantioselectivity, diastereoselectivity. In addition to the diverse 1-ketocarbonyl-3-substituted BCBs, α/β-substituted are compatible such an unprecedented photoredox catalytic pathway, resulting in successful assembly all-carbon quaternary stereocenter or two adjacent tertiary stereocenters on product.

Language: Английский

Citations

68
Asymmetric Cross-Coupling of Aldehydes with Diverse Carbonyl or Iminyl Compounds by Photoredox-Mediated Cobalt Catalysis DOI

Zhiyong Chi,

Jia-Bin Liao,

Xiuliang Cheng

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10857 - 10867

Published: April 8, 2024

The asymmetric cross-coupling of unsaturated bonds, hampered by their comparable polarity and reactivity, as well the scarcity efficient catalytic systems capable diastereo- enantiocontrol, presents a significant hurdle in organic synthesis. In this study, we introduce highly adaptable photochemical cobalt catalysis framework that facilitates chemo- stereoselective reductive cross-couplings between common aldehydes with broad array carbonyl iminyl compounds, including N-acylhydrazones, aryl ketones, aldehydes, α-keto esters. Our methodology hinges on synergistic mechanism driven photoredox-induced single-electron reduction subsequent radical–radical coupling, all precisely guided chiral catalyst. Various optically enriched β-amino alcohols unsymmetrical 1,2-diol derivatives (80 examples) have been synthesized good yields (up to 90% yield) high stereoselectivities >20:1 dr, 99% ee). Of particular note, approach accomplishes unattainable transformations disparate partners without reliance any external photosensitizer, thereby further emphasizing its versatility cost-efficiency.

Language: Английский

Citations

17
Catalytic Asymmetric Redox‐Neutral [3+2] Photocycloadditions of Cyclopropyl Ketones with Vinylazaarenes Enabled by Consecutive Photoinduced Electron Transfer DOI

Wenhui Wei,

Chunyang Li, Yifan Fan

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: April 30, 2024

Abstract Consecutive photoinduced electron transfer (ConPET) is a powerful and atom‐economical protocol to overcome the limitations of intrinsic redox potential visible light‐absorbing photosensitizers, thereby considerably improving substrate reaction types. Likely because such an exothermic single‐electron (SET) process usually does not require aid chiral catalysts, resulting in inevitable racemic background reaction, notably, no enantioselective manifolds have been reported. Herein, we report on viability cooperative ConPET hydrogen‐bonding catalysis for [3+2] photocycloaddition cyclopropyl ketones with vinylazaarenes. In addition enabling first use olefins that preferentially interact this platform paves way efficient synthesis pharmaceutically synthetically important cyclopentyl functionalized by azaarenes high yields, ees dr. The robust capacity method can be further highlighted low loading catalyst (1.0 mol %), good compatibility both 2‐azaarene 3‐pyridine‐based olefins, successful concurrent construction three stereocenters cyclopentane rings involving elusive but all‐carbon quaternary.

Language: Английский

Citations

11
Enantioselective [2 + 2] Photocycloreversion Enables De Novo Deracemization Synthesis of Cyclobutanes DOI
Jiahao Wang,

Qianqian Fu,

Shanshan Cao

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22840 - 22849

Published: Aug. 2, 2024

While photochemical deracemization significantly enhances atom economy by eliminating the necessity for additional oxidants or reductants, laborious presynthesis of substrates from feedstock chemicals is often required, thereby compromising practicality this method. In study, we propose a novel approach known as de novo synthesis, which involves direct utilization simple undergoing both transformation and reversible transformation. The efficient enantiocontrol chiral catalysts in latter process establishes an effective platform deracemization. This alternative practical to address challenges asymmetric photocatalysis has been successfully demonstrated photosensitized synthesis azaarene-functionalized cyclobutanes featuring three stereocenters, including all-carbon quaternary center. By exclusively employing suitable catalyst enable kinetically controlled [2 + 2] photocycloreversion, pave creative path toward achieving more cost-effective

Language: Английский

Citations

8
Asymmetric Photoredox Catalytic Minisci-Type Reactions of α-Bromide Amides DOI
Qifu Li, Xiaowei Zhao, Yanli Yin

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: 27(5), P. 1244 - 1249

Published: Jan. 23, 2025

An asymmetric photoredox catalytic Minisci-type reaction between α-bromide amides and imine-containing azaarenes has been successfully developed. This catalyst system employs a chiral phosphoric acid alongside 3DPAFIPN as photosensitizer. The produces diverse array of valuable amides, featuring azaarene-substituted tertiary carbon stereocenters at the β-position, in high yields (up to 85%) good excellent enantioselectivities >99% enantiomeric excess (ee)). Importantly, this work marks first example radical addition simple utilizing radicals functionalized with electron-withdrawing carbonyl groups, which are conventionally considered unfavorable for such transformations, especially an enantioselective manner.

Language: Английский

Citations

1
Catalytic asymmetric photocycloaddition reactions mediated by enantioselective radical approaches DOI
Yanli Yin,

Mengdi You,

Xiangtao Li

et al.

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

The use of olefins in the construction cyclic compounds represents a powerful strategy for advancing pharmaceutical industry.

Language: Английский

Citations

1
Chiral Primary Amine-Catalyzed Asymmetric Photochemical Reactions of Pyridotriazoles with Boronic Acids to Access Triarylmethanes DOI
Chenyang Jiang,

Youlan Meng,

Yalei Huang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 29, 2025

Imine-containing azaarene-based triarylmethanes are vital molecular motifs that prevalent in a wide array of bioactive compounds. Recognizing the limitations current synthetic methodologies─marked by scarcity examples and difficulties flexible functional group modulation─we have developed an efficient modular asymmetric photochemical strategy employing pyridotriazoles boronic acids as substrates. Utilizing novel chiral diamine-derived pyrroles primary amines catalysts, we successfully synthesized diverse range with high yields excellent enantioselectivities. This method not only exhibits broad substrate scope outstanding tolerance but also enables precise synthesis deuterated derivatives using inexpensive D2O deuterium source. Mechanistic studies reveal unusual 1,4-boron shift is critical step generating boronated enamine intermediate, while shedding light on potential enantiocontrol mechanisms facilitated catalyst.

Language: Английский

Citations

1
Chemodivergent Synthesis of Benzofurans and 2,3‐Dihydrobenzofurans via Tandem Oxidative Annulation of Enaminones and Salicylaldehydes DOI
Xiyan Duan, Hui Li, Junqi Wang

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(15), P. 1727 - 1733

Published: March 26, 2024

Comprehensive Summary Chemodivergent synthesis of benzofurans and 2,3‐dihydrobenzofurans has been realized. Under a reaction system consisting DBDMH K 2 CO 3 as promotors, controlled conditions enabled the formation two sets valuable heterocycles from tandem transformation enaminones salicylaldehydes. The key to success was identification parameters, in which imine intermediate formed by transient halogenation coupling substitution processes underwent either aldol condensation/annulation or hydrolysis/aldol condensation. additives NH 4 Cl Fe (SO ) unique selectivity this reaction. A broad substrate scope salicylaldehydes employed reaction, demonstrating excellent functional group tolerance versatility.

Language: Английский

Citations

7
Catalytic asymmetric [4 + 2] dearomative photocycloadditions of anthracene and its derivatives with alkenylazaarenes DOI Creative Commons
Dong Tian,

Wenshuo Shi,

Xin Sun

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 29, 2024

Abstract Photocatalysis through energy transfer has been investigated for the facilitation of [4 + 2] cycloaddition reactions. However, high reactivity radical species poses a challenging obstacle to achieving enantiocontrol with chiral catalysts, as no enantioselective examples have reported thus far. Here, we present development catalytic asymmetric dearomative photocycloaddition involving anthracene and its derivatives alkenylazaarenes. This accomplishment is achieved by utilizing cooperative photosensitizer Brønsted acid catalysis platform. Importantly, this process enables activation substrates from triplet DPZ, thereby initiating precise stereoselective sequential transformation. The significance our work highlighted synthesis diverse range pharmaceutical valuable cycloadducts incorporating attractive azaarenes, all obtained yields, ees, drs. broad substrate scope further underscored successful construction all-carbon quaternary stereocenters adjacent stereocenters.

Language: Английский

Citations

7
Sequential C−F Bond Transformation of the Difluoromethylene Unit in Perfluoroalkyl Groups: A Combination of Fine‐Tuned Phenothiazine Photoredox Catalyst and Lewis Acid DOI Creative Commons
Naoki Sugihara, Yoshihiro Nishimoto, Yasuko Osakada

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Feb. 21, 2024

A sequential process via photoredox catalysis and Lewis acid mediation for C-F bond transformation of the CF

Language: Английский

Citations

5