Figure - available from: Nature Communications
This content is subject to copyright. Terms and conditions apply.
Transition-metal-catalyzed asymmetric coupling reactions to synthesize NSAID derivatives a The classical asymmetric cross-coupling with organometallic reagents. b Transition metal catalyzed asymmetric arylation of enol silane derivatives. c Nickel-photoredox co-catalyzed asymmetric reductive arylation of racemic α-chloro esters. d A complementary photoredox/nickel catalyzed enantioselective carboarylation of alkenes. e This work: Nickel/photoredox catalyzed reductive asymmetric alky arylation of acrylates.
Source publication
Nonsteroidal anti-inflammatory drug derivatives (NSAIDs) are an important class of medications. Here we show a visible-light-promoted photoredox/nickel catalyzed approach to construct enantioenriched NSAIDs via a three-component alkyl arylation of acrylates. This reductive cross-electrophile coupling avoids preformed organometallic reagents and rep...
Contexts in source publication
Context 1
... asymmetric cross-coupling between α-halo esters and organometallic reagents (e.g., Grignard, organozinc, organoboron, and organosilicon) (Fig. 1a) was developed and driven mainly by G.C. Fu and coworkers [6][7][8][9] . A complementary approach was reported by Zhou 10 and Gaunt 11 involving asymmetric arylation of enol silane derivatives with aryl sulfonates or iodonium salts under enantioselective transition metal catalysis (Fig. 1b). Motivated by a desire to broaden the scope of ...Context 2
... Grignard, organozinc, organoboron, and organosilicon) (Fig. 1a) was developed and driven mainly by G.C. Fu and coworkers [6][7][8][9] . A complementary approach was reported by Zhou 10 and Gaunt 11 involving asymmetric arylation of enol silane derivatives with aryl sulfonates or iodonium salts under enantioselective transition metal catalysis (Fig. 1b). Motivated by a desire to broaden the scope of coupling partners while also avoiding moistureand air-sensitive organometallic reagents, Reisman [12][13][14][15][16] , Doyle 17 , Weix 18 , and their groups developed nickel catalyzed asymmetric reductive cross-electrophile coupling reactions using stoichiometric metal reductants (Zn or ...Context 3
... , Weix 18 , and their groups developed nickel catalyzed asymmetric reductive cross-electrophile coupling reactions using stoichiometric metal reductants (Zn or Mn). Inspired by their elegant studies, we disclosed an example of highly enantioselective nickel-photoredox catalyzed reductive cross-coupling of racemic α-chloro esters with aryl iodides (Fig. 1c) to construct enantioenriched NSAID derivatives 19 . Building on this work, we envisioned intercepting intermediates along the enantioselective cross-electrophile coupling reaction pathway with an olefin insertion step. Such a strategy could potentially lead to valuable enantioenriched olefin difunctionalization ...Context 4
... enantioselective threecomponent reactions were developed by Diao 28 , Chu 29,30 , Nevado 31 as well as others [32][33][34][35][36][37][38] . In the final stages of preparing this manuscript, a complementary enantioselective three-component carboarylation of alkenes with alkyltrifluoroborates and aryl bromides was disclosed by Gutierrez and Chu 29 (Fig. 1d). The redox-neutrality of this method is counterbalanced by the use of alkyltrifluoroborates, which must be prepared ...Context 5
... this work, we present an example of enantioselective domino alky arylation of acrylates with alkyl-and aryl-bromides via cooperative nickel and photoredox catalysis (Fig. 1e). The organic photoredox 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene (4CzIPN) acts as "pseudoreductant" with Hantzsch ester (HEH) as the terminal electron donor. The products of this cascade process are NSAID derivatives of potential use in medicinal ...Citations
... However, controlling the enantioselectivity of the generated stereogenic centres remains a formidable challenge owing to the high reactivity and instability of the open shell radical intermediates participating in these transformations. Chiral copper [37][38][39][40][41][42][43] and nickel [44][45][46][47][48][49][50][51][52] complexes have opened a robust platform for asymmetric radical conjunctive cross-coupling of olefins. For example, impressive progress has been made in nickel-catalysed asymmetric radical relayed reductive coupling [46][47][48][49] , in which C(sp 3 )-hybridized electrophiles such as alkyl halides and perfluoroalkyl halides have been employed as radical precursors. ...
... Chiral copper [37][38][39][40][41][42][43] and nickel [44][45][46][47][48][49][50][51][52] complexes have opened a robust platform for asymmetric radical conjunctive cross-coupling of olefins. For example, impressive progress has been made in nickel-catalysed asymmetric radical relayed reductive coupling [46][47][48][49] , in which C(sp 3 )-hybridized electrophiles such as alkyl halides and perfluoroalkyl halides have been employed as radical precursors. In addition, processes merging photoredox catalysis and nickel catalysis have enabled the asymmetric redox-neutral dicarbofunctionalization of alkenes with alkyltrifluoroborates as competent synthons for these protocols 50,51 . ...
... The scope of C-H precursors was explored next (Fig. 4). As expected, cycloalkanes with various ring sizes such as cyclopentane (46), cycloheptane (47), cyclooctane (48) and cyclododecane (49) were well tolerated. In the last case, because of the lack of solubility of the reagent, an e.r. of 91:9 was obtained under standard reaction conditions, which was improved to 96:4 by increasing the amount of solvent and the use of L5 as ligand. ...
The development of novel strategies to rapidly construct complex chiral molecules from readily available feedstocks is a long-term pursuit in the chemistry community. Radical-mediated alkene difunctionalizations represent an excellent platform towards this goal. However, asymmetric versions remain highly challenging, and more importantly, examples featuring simple hydrocarbons as reaction partners are elusive. Here we report an asymmetric three-component alkene dicarbofunctionalization capitalizing on the direct activation of C(sp³)–H bonds through the combination of photocatalysed hydrogen atom transfer and nickel catalysis. This protocol provides an efficient platform for installing two vicinal carbon–carbon bonds across alkenes in an atom-economic fashion, providing a wide array of high-value chiral α-aryl/alkenyl carbonyls and phosphonates, as well as 1,1-diarylalkanes from ubiquitous alkane, ether and alcohol feedstocks. This method exhibits operational simplicity, broad substrate scope and excellent regioselectivity, chemoselectivity and enantioselectivity. The compatibility with bioactive motifs and expedient synthesis of pharmaceutically relevant molecules highlight the synthetic potential of this protocol.
... The nickel/photoredox dual catalysis system has been developed as a powerful tool in the C − C bonds cross-coupling because of its high efficiency and mildness, as well as its green properties [31][32][33][34] . The nickel/photoredox catalytic dicarbofunctionalization was also successfully exploited to formulate two vicinal C − C bonds in one step, albeit mainly focused on electronically biased alkenes with directing groups or coordinating groups (Fig. 1a) [35][36][37][38][39][40][41][42][43][44][45][46] . In contrast, the nickel/photoredox catalytic dicarbofunctionalization of nonactivated alkenes presents a tremendous challenge because of their low reaction activities, giving rise to weak catalytic efficiency and more side reactions 38 . ...
Alkene dicarbofunctionalization is an efficient strategy and operation-economic fashion for introducing complexity in molecules. A nickel/photoredox dual catalyzed arylalkylation of nonactivated alkenes for the simultaneous construction of one C(sp³)−C(sp³) bond and one C(sp³)−C(sp²) bond has been developed. The mild catalytic method provided valuable indanethylamine derivatives with wide substrate scope and good functional group compatibility. An enantioselective dicarbofunctionalization was also achieved with pyridine-oxazoline as a ligand. The efficiency of metallaphotoredox dicarbofunctionalization was demonstrated for the concise synthesis of pharmaceutically active compounds.
Chiroptical response, demonstrating chiral interaction between optical vortex and chiral structure, plays an important role in variety of fields like optics and material science. However, the flexibility and efficiency of chiral structure fabrication are limited due to mask requirement and a point‐by‐point constructing strategy. In this paper, a novel chiral lithography method is proposed that utilizes optical vortex phase beam shaping to achieve chiral structure processing with high efficiency and flexibility. By programming topological charges of the vortex phase, chiral structures with adjustable appearance, rotation, and chirality can be produced using femtosecond laser single pulse exposure. Transmittance measurements of fabricated chiral structures array confirm a 66% helical dichroism that is predicted by simulation. Moreover, with the aid of convolutional neural networks (CNN), an accuracy of 98% in Orbital Angular Momentum (OAM) recognition can be achieved. This chiral lithography method provides an alternative for chiral structure fabrication and holds promise in the development of chiral optics, optical communications, and next‐generation optical devices.
