A dual light-driven palladium catalyst: Breaking the barriers in carbonylation reactions

Science ◽  
2020 ◽  
Vol 368 (6488) ◽  
pp. 318-323 ◽  
Author(s):  
Gerardo M. Torres ◽  
Yi Liu ◽  
Bruce A. Arndtsen
Keyword(s):  
Bond Cleavage ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Coupling Reactions ◽  
Ambient Conditions ◽  
Inherent Limitation ◽  
Carbonyl Derivatives ◽  
Palladium Catalyzed ◽  
Light Excitation ◽  
Metal Catalyzed

Transition metal–catalyzed coupling reactions have become one of the most important tools in modern synthesis. However, an inherent limitation to these reactions is the need to balance operations, because the factors that favor bond cleavage via oxidative addition ultimately inhibit bond formation via reductive elimination. Here, we describe an alternative strategy that exploits simple visible-light excitation of palladium to drive both oxidative addition and reductive elimination with low barriers. Palladium-catalyzed carbonylations can thereby proceed under ambient conditions, with challenging aryl or alkyl halides and difficult nucleophiles, and generate valuable carbonyl derivatives such as acid chlorides, esters, amides, or ketones in a now-versatile fashion. Mechanistic studies suggest that concurrent excitation of palladium(0) and palladium(II) intermediates is responsible for this activity.

DFT Study of the Mechanisms of Transition-Metal-Catalyzed Reductive Coupling Reactions

2020 ◽  
Vol 24 (12) ◽  
pp. 1367-1383
Author(s):  
Yuling Wang ◽  
Qinghua Ren
Keyword(s):  
Transition Metal ◽  
Density Functional ◽  
Single Point ◽  
Oxidative Addition ◽  
Density Functional Theory Calculations ◽  
Reductive Elimination ◽  
Coupling Reactions ◽  
Reductive Coupling ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

The mechanism studies of transition-metal-catalyzed reductive coupling reactions investigated using Density Functional Theory calculations in the recent ten years have been reviewed. This review introduces the computational mechanism studies of Ni-, Pd-, Cu- and some other metals (Rh, Ti and Zr)-catalyzed reductive coupling reactions and presents the methodology used in these computational mechanism studies. The mechanisms of the transition- metal-catalyzed reductive coupling reactions normally include three main steps: oxidative addition; transmetalation; and reductive elimination or four main steps: the first oxidative addition; reduction; the second oxidative addition; and reductive elimination. The ratelimiting step is most likely the final reductive elimination step in the whole mechanism. Currently, the B3LYP method used in DFT calculations is the most popular choice in the structural geometry optimizations and the M06 method is often used to carry out single-point calculations to refine the energy values. We hope that this review will stimulate more and more experimental and computational combinations and the computational chemistry will significantly contribute to the development of future organic synthesis reactions.

Pharmaceutical diversification via palladium oxidative addition complexes

Science ◽  
2019 ◽  
Vol 363 (6425) ◽  
pp. 405-408 ◽  
Author(s):  
Mycah R. Uehling ◽  
Ryan P. King ◽  
Shane W. Krska ◽  
Tim Cernak ◽  
Stephen L. Buchwald
Keyword(s):  
Chemical Space ◽  
Oxidative Addition ◽  
Cross Coupling ◽  
Catalytic Reactions ◽  
Coupling Reactions ◽  
Chemical Probes ◽  
Ambient Conditions ◽  
Cross Coupling Reactions ◽  
Alternative Approach ◽  
Palladium Catalyzed

Palladium-catalyzed cross-coupling reactions have transformed the exploration of chemical space in the search for materials, medicines, chemical probes, and other functional molecules. However, cross-coupling of densely functionalized substrates remains a major challenge. We devised an alternative approach using stoichiometric quantities of palladium oxidative addition complexes (OACs) derived from drugs or drug-like aryl halides as substrates. In most cases, cross-coupling reactions using OACs proceed under milder conditions and with higher success than the analogous catalytic reactions. OACs exhibit remarkable stability, maintaining their reactivity after months of benchtop storage under ambient conditions. We demonstrated the utility of OACs in a variety of experiments including automated nanomole-scale couplings between an OAC derived from rivaroxaban and hundreds of diverse nucleophiles, as well as the late-stage derivatization of the natural product k252a.

Dearomatization–Rearomatization Strategy for Palladium-Catalyzed C–N Cross-Coupling Reactions

Synlett ◽  
2020 ◽  
Author(s):  
Chao-Jun Li ◽  
Huiying Zeng ◽  
Yatao Lang
Keyword(s):  
Organic Chemistry ◽  
Aromatic Compounds ◽  
Bond Cleavage ◽  
Cross Coupling ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Diphenyl Ethers ◽  
Palladium Catalyzed ◽  
History Of ◽  
Metal Catalyzed

AbstractSubstituted aromatic compounds play important roles in materials, biological agents, dyes, etc. Thus, the synthesis of substituted aromatic compounds has been a hot topic throughout the history of organic chemistry. Traditionally, the Friedel–Crafts reaction was a powerful tool for synthesizing substituted aromatic compounds. In recent decades, metal-catalyzed cross-coupling reactions were well developed via carbon–heteroatom bond cleavage, however, having difficulties towards some strong bonds, such as C(Ar)–OH. To overcome such challenges, newer strategies are needed. In this review, we summarize the recent efforts in the development of dearomatization–rearomatization strategy for cross-coupling reactions via C(Ar)–O bond cleavage.1 Introduction2 Dearomatization–Rearomatization Strategy for Cross-Coupling of Phenols3 Dearomatization–Rearomatization Strategy for Cross-Coupling of Biphenols4 Dearomatization–Rearomatization Strategy for Cross-Coupling of Diphenyl Ethers5 Dearomatization–Rearomatization Strategy for Cross-Coupling of Indoles6 Summary

Palladium-Catalyzed Carbonylative Coupling Reactions of N ,N -Bis(methanesulfonyl)amides through C-N Bond Cleavage

2018 ◽  
Vol 2018 (41) ◽  
pp. 5717-5724 ◽  
Author(s):  
Minkyung Lim ◽  
Hyeji Kim ◽  
Jaeyoung Ban ◽  
Junghan Son ◽  
Jae Kyun Lee ◽  
...  
Keyword(s):  
Bond Cleavage ◽  
Coupling Reactions ◽  
Palladium Catalyzed

Transition-Metal-Catalyzed Cross-Coupling with Non-Diazo Carbene Precursors

Synlett ◽  
2018 ◽  
Vol 30 (05) ◽  
pp. 542-551 ◽  
Author(s):  
Jianbo Wang ◽  
Kang Wang
Keyword(s):  
Transition Metal ◽  
Cross Coupling ◽  
Diazo Compounds ◽  
Coupling Reactions ◽  
Cross Coupling Reactions ◽  
Carbon Carbon Bond ◽  
Palladium Catalyzed ◽  
Fischer Carbenes ◽  
Transition Metal Catalyzed ◽  
Metal Catalyzed

Transition-metal-catalyzed cross-coupling reactions through metal carbene migratory insertion have emerged as powerful methodology for carbon–carbon bond constructions. Typically, diazo compounds (or in situ generated diazo compounds from N-tosylhydrazones) have been employed as the metal carbene precursors for this type of cross-coupling reactions. Recently, cross-coupling reactions employing non-diazo carbene precursors, such as conjugated ene-yne-ketones, allenyl ketones, alkynes, cyclopropenes, and Cr(0) Fischer carbenes, have been developed. This account will summarize our efforts in the development of transition-metal-catalyzed cross-coupling reactions with these non-diazo carbene precursors.1 Introduction2 Cross-Coupling with Ene-yne-ketones, Allenyl Ketones, and Alkynes3 Cross-Coupling Involving Ring-Opening of Cyclopropenes4 Palladium-Catalyzed Cross-Coupling with Chromium(0) Fischer Carbenes5 Conclusion

Organoboron compounds as mild nucleophiles in Lewis acid- and transition metal-catalyzed C­C bond-forming reactions

2002 ◽  
Vol 74 (1) ◽  
pp. 43-55 ◽  
Author(s):  
Robert A. Batey ◽  
Tan D. Quach ◽  
Ming Shen ◽  
Avinash N. Thadani ◽  
David V. Smil ◽  
...  
Keyword(s):  
Lewis Acid ◽  
Coupling Reactions ◽  
Rhodium Catalysis ◽  
Organoboron Compounds ◽  
Bond Forming ◽  
Acyliminium Ions ◽  
Cross Coupling Reactions ◽  
Bond Forming Reactions ◽  
Palladium Catalyzed ◽  
Metal Catalyzed

The use of air- and water-stable organoboron compounds for C­C bond-forming reactions are reported. These studies include the Lewis acid-promoted additions of boronic esters to N-acyliminium ions and allyl and crotyltrifluoroborate salts to aldehydes. Aryl and alkenyltrifluoroborate salts will add to aldehydes under the influence of rhodium catalysis or in the presence of zinc metal. These salts also participate in palladium-catalyzed Suzuki­Miyaura and other cross-coupling reactions. Finally, a new type of N-heterocyclic carbene ligand is reported and used for Pd-catalyzed Suzuki­Miyaura couplings.

Oxidative addition of monosilanes to planar iridium(I) complexes and carbonylation of the resulting adducts

1977 ◽  
Vol 30 (6) ◽  
pp. 1201 ◽  
Author(s):  
MA Bennett ◽  
R Charles ◽  
PJ Fraser
Keyword(s):  
Carbon Monoxide ◽  
Oxidative Addition ◽  
Reductive Elimination ◽  
Steric Effects ◽  
Ambient Conditions ◽  
Tetragonal Pyramidal ◽  
Group 5 ◽  
Electronic And Steric Effects

Silanes [R3SiH; R3 = Cl3, MeCl2, (EtO)3, Ph3] undergo irreversible oxidative addition to planar iridium(I) complexes IrClL3 (L = PPh3, PMePh2 or AsPh3) to give silyliridium(III) hydrides IrHCl(SiR3)Ln (n = 2 or 3). The yellow, five-coordinate, probably tetragonal pyramidal complexes(n = 2) are formed mainly when L = PPh3 or AsPh3, and also in the case of L = PmePh2, R = Ph, whereas the colourless, six-coordinate, presumably octahedral adducts are formed predominantly when L = PMePh2. Both five- and six-coordinate adducts can be isolated from the addition of dichloro(methyl)silane to IrCl(AsPh3)3. Most of the adducts react with carbon monoxide under ambient conditions to give silyliridium(III) hydrido carbonyls, IrHCl(SiR3)(CO)L2, which may undergo partial or complete reductive elimination to IrCl(CO)L2 and R3SiH; the ease with which this occurs depends on L (PPh3 > PMePh2 > AsPh3) and on R3 [Ph3 > (EtO)3 > Cl3 ≈ MeCl2]. The reactions of silanes with IrClL3, RhClL3 and IrCl(CO)(PPh3)2 are compared, and the trends observed in the case of IrClL3 are discussed in terms of electronic and steric effects in the silyl and Group 5 donors. Structural assignments for the new complexes are based on i.r., far-i.r. and 1H N.M.R. data.

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