Cooperative Coupling of Oxidative Organic Synthesis and Hydrogen Production over Semiconductor-Based Photocatalysts

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(21), P. 13051 - 13085

Published: Aug. 11, 2021

Merging hydrogen (H2) evolution with oxidative organic synthesis in a semiconductor-mediated photoredox reaction is extremely attractive because the clean H2 fuel and high-value chemicals can be coproduced under mild conditions using light as sole energy input. Following this dual-functional photocatalytic strategy, dreamlike pathway for constructing C–C/C–X (X = C, N, O, S) bonds from abundant readily available X–H bond-containing compounds concomitant release of fulfilled without need external chemical reagents, thus offering green fascinating synthetic strategy. In review, we begin by presenting concise overview on general background traditional production then focus fundamental principles cooperative coupling selective simultaneous utilization photoexcited electrons holes over semiconductor-based catalysts to meet economic sustainability goal. Thereafter, put dedicated emphasis recent key progress various transformations, including alcohol oxidation, methane conversion, amines coupling, cross-coupling, cyclic alkanes dehydrogenation, reforming lignocellulosic biomass, so on. Finally, remaining challenges future perspectives flourishing area have been critically discussed. It anticipated that review will provide enlightening guidance rational design such system, thereby stimulating development economical environmentally benign solar generation value-added fine chemicals.

Language: Английский

---

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(8), P. 4373 - 4505

Published: March 19, 2021

This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution decarboxylative oxidative substitutions. For each reaction, catalytic data, as well examples of their application to synthesis complex molecules, are collected. Sections which we discuss key aspects for high selectivity a comparison with other metals (with advantages disadvantages) also included. asymmetric substitution, data grouped according type nucleophile employed. Because prominent position use stabilized carbon nucleophiles heteronucleophiles, many chiral ligands have been developed. To better compare results, they presented by ligand types. reactions mainly promoted PHOX or Trost ligands, justifies organizing this section chronological order. results used.

Language: Английский

---

Iridium-Catalyzed Asymmetric Synthesis of Functionally Rich Molecules Enabled by (Phosphoramidite,Olefin) Ligands

Accounts of Chemical Research, Journal Year: 2019, Volume and Issue: 52(9), P. 2657 - 2672

Published: June 19, 2019

ConspectusThe catalytic, asymmetric synthesis of complex molecules has been a core focus our research program for some time because developments in the area can have an immediate impact on identification novel strategies value-added molecules. In concert with this central interest, we emphasized design ligand scaffolds as tactic to discover and develop chemistry overcome well-recognized synthetic challenges. Based group's work chiral pool-derived diolefin ligands, designed implemented class hybrid (phosphoramidite,olefin) which combines properties both phosphoramidite olefin motifs impact, fine-tune, even override inherent reactivity metal center. Specifically, utilized these unique modifying ligands address several recognized limitations field iridium-catalyzed, allylic substitution. The methods documented typically employ branched, unprotected alcohols substrates obviate need rigorous exclusion air moisture.Following Takeuchi's seminal report demonstrating high aptitude Ir(I)-phosphite catalysts branch-selective substitution, concerted efforts from numerous laboratories led broadening utility reaction class. first section Account outlines process leading discovery unprecedented its validation iridium-catalyzed amination alcohols. This continues involving heteroatom-based nucleophiles within inter- intramolecular etherification, thioetherification spiroketalization processes. second highlights use readily available carbon possessing sp, sp2, sp3 hybridization series enantioselective carbon–carbon bond-forming reactions. We describe how alkylzinc, allylsilane, classes organotrifluoroborate be coupled enantioselectively enable construction key including 1,5-dienes, 1,4-dienes, 1,4-enynes. Since electronic steric renders (η3-allyl)-Ir(III) intermediate highly electrophilic, weak such alkyl olefins used. also show that more nucleophilic alkene enamines situ generated ketene acetals smoothly participate substitution reactions yield valuable piperidines γ,δ-unsaturated esters, respectively.The concept stereodivergent dual catalysis, synergistically amine catalysis iridium furnish α-allylated aldehydes containing two independently controllable stereocenters is then discussed. enabled independent, stereoselective all four possible product stereoisomers single set starting materials, was highlighted Δ9-tetrahydrocannabinol. concludes overview organometallic mechanistic studies regarding relevant intermediates catalytic cycle These allowed us better understand origin characteristics exhibited by catalyst comparison related systems.

Language: Английский

---

Asymmetric synthesis of allylic compoundsviahydrofunctionalisation and difunctionalisation of dienes, allenes, and alkynes

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(7), P. 2060 - 2118

Published: Jan. 1, 2020

This review article provides an overview of progress in asymmetric synthesis allylic compoundsviahydrofunctionalisation and difunctionalisation dienes, allenes, alkynes.

Language: Английский

---

Advances in Catalytic Asymmetric Dearomatization

ACS Central Science, Journal Year: 2021, Volume and Issue: 7(3), P. 432 - 444

Published: Feb. 22, 2021

Asymmetric catalysis has been recognized as the most enabling strategy for accessing chiral molecules in enantioenriched forms. Catalytic asymmetric dearomatization is an emerging and dynamic research subject catalysis, which received considerable attention recent years. The direct transformations from readily available aromatic feedstocks to structurally diverse three-dimensional polycyclic make catalytic reactions of broad interest both organic synthesis medicinal chemistry. However, inherent difficulty disruption aromaticity demands a large energy input during process, might be incompatible with conditions generally required by catalysis. In this Outlook, we will discuss representative strategies examples various compounds try convince readers that overcoming above obstacles, could advance chemical sciences many respects.

Language: Английский

---

Enantioselective Formation of Quaternary Centers by Allylic Alkylation with First-Row Transition-Metal Catalysts

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(7), P. 4084 - 4099

Published: Feb. 11, 2021

Asymmetric allylic alkylation mediated by transition metals provides an efficient strategy to form quaternary stereogenic centers. While this transformation is dominated the use of second- and third-row (e.g., Pd, Rh, Ir), recent developments have revealed potential first-row metals, which provide not only a less expensive potentially equally alternative but also new mechanistic possibilities. This review summarizes examples for assembly stereocenters using prochiral substrates hard, achiral nucleophiles in presence copper complexes highlights complementary approaches with soft, catalyzed chiral cobalt nickel complexes.

Language: Английский

---

Diastereodivergent synthesis of enantioenriched α,β-disubstituted γ-butyrolactones via cooperative N-heterocyclic carbene and Ir catalysis

Nature Catalysis, Journal Year: 2019, Volume and Issue: 3(1), P. 48 - 54

Published: Dec. 2, 2019

Language: Английский

---

Catalytic Enantioselective Functionalizations of C–H Bonds by Chiral Iridium Complexes

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(18), P. 10516 - 10543

Published: Sept. 8, 2020

The development of catalytic enantioselective transformations, enabling the construction complex molecular scaffolds from simple precursors, has been a long-standing challenge in organic synthesis. Recent achievements transition-metal catalyzed functionalizations carbon–hydrogen (C–H) bonds represent promising pathway toward this goal. Over last two decades, iridium catalysis evolved as valuable tool stereocontrolled synthesis chiral molecules via C–H activation. iridium-based systems with various ligand classes, well studies their reaction mechanisms, resulted dynamic progress area. This review aims to present comprehensive picture by complexes emphasis on mechanisms activation step.

Language: Английский

---

Catalytic Asymmetric Reactions with N-Metallated Azomethine Ylides

Accounts of Chemical Research, Journal Year: 2020, Volume and Issue: 53(5), P. 1084 - 1100

Published: April 22, 2020

ConspectusOptically active nitrogen-containing compounds have attracted substantial attention due to their ubiquity in the cores of natural products and bioactive molecules. Among various synthetic approaches nitrogenous frameworks, catalytic asymmetric 1,3-dipolar cycloadditions are one most attractive methods because powerful ability rapidly construct chiral N-heterocycles. In particular, N-metallated azomethine ylides, common readily available 1,3-dipoles, been extensively applied dipolar cycloaddition reactions. Despite fact that transformations ylides investigated for decades, efforts directed toward preparation pyrrolidines using glycinate-derived α-unsubstituted aldimine esters as precursors ylides. While α-substituted derived from amino other than glycinate seldom harnessed, construction non-five-membered N-heterocycles via remains underexplored. addition, α-functionalization prepare acyclic such α-amino acids, which an situ-generated ylide serves nucleophile, has not sufficiently described.In this Account, we mainly discuss achievements made past decade broadening applications compounds. We began our investigation with design synthesis a new type ligand, TF-BiphamPhos, only coordinates Lewis acids activate species but also H-bond donor increase reactivity dipolarophiles significantly enhanced stereochemical control. Using Cu(I) or Ag(I)/TF-BiphamPhos complex catalyst, achieved highly stereoselective (3+2) non-glycinate-derived diverse dipolarophiles, producing variety enantioenriched multiple stereocenters single step. To further expand utility successfully developed higher order fulvenes, tropone, 2-acyl cycloheptatrienes, pyrazolidinium serving reaction partner, provides straightforward access fused piperidines, bridged azabicyclic triazines (3+6)- (3+3)-type cycloadditions. realized Cu(I)-catalyzed 1,4-Michael additions α,β-unsaturated bisphosphates/Morita–Baylis–Hillman products, furnishing array structurally unnatural acids. Based on strategy synergistic activation, efficient dual Cu/Pd Cu/Ir catalysis allylic/allenylic alkylation Notably, allowed stereodivergent α,α-disubstituted branched allylic reaction, two distinct metal catalysts independently full control over corresponding nucleophile electrophile. Furthermore, expedient biologically important tetrahydro-γ-carbolines was through Cu/Ir-catalyzed cascade allylation/iso-Pictet–Spengler cyclization. when steric congestion allylation intermediates increased, combined provided allylation/2-aza-Cope rearrangement, optically homoallylic amines impressive results.

Language: Английский

---

Transition metal-catalysed allylic functionalization reactions involving radicals

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(17), P. 6186 - 6197

Published: Jan. 1, 2020

In this tutorial review, different types of transition metal-catalysed allylic functionalization reactions involving radicals are highlighted.

Language: Английский

---