Feedstock Reagents in Metal‐Catalyzed Carbonyl Reductive Coupling: Minimizing Preactivation for Efficiency in Target‐Oriented Synthesis

2019 ◽  
Vol 131 (40) ◽  
pp. 14193-14202 ◽  
Author(s):  
Rosalie S. Doerksen ◽  
Cole C. Meyer ◽  
Michael J. Krische
Keyword(s):  
Reductive Coupling ◽  
Metal Catalyzed

scholarly journals Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition

Science ◽  
2016 ◽  
Vol 354 (6310) ◽  
pp. aah5133 ◽  
Author(s):  
Khoa D. Nguyen ◽  
Boyoung Y. Park ◽  
Tom Luong ◽  
Hiroki Sato ◽  
Victoria J. Garza ◽  
...  
Keyword(s):  
Reductive Coupling ◽  
Carbonyl Addition ◽  
Metal Catalyzed

Recent Developments in C–C Bond Formation Using Catalytic Reductive Coupling Strategies

Synthesis ◽  
2020 ◽  
Vol 52 (18) ◽  
pp. 2623-2638
Author(s):  
Joshua D. Sieber ◽  
Toolika Agrawal
Keyword(s):  
Bond Formation ◽  
Cross Coupling ◽  
Short Review ◽  
Reductive Coupling ◽  
Recent Developments ◽  
Molecular Complexity ◽  
Metal Catalyzed ◽  
Coupling Processes ◽  
Coupling Strategies

Metal-catalyzed reductive coupling processes have emerged as a powerful methodology for the introduction of molecular complexity from simple starting materials. These methods allow for an orthogonal approach to that of redox-neutral strategies for the formation of C–C bonds by enabling cross-coupling of starting materials not applicable to redox-neutral chemistry. This short review summarizes the most recent developments in the area of metal-catalyzed reductive coupling utilizing catalyst turnover by a stoichiometric reductant that becomes incorporated in the final product.1 Introduction2 Ni Catalysis3 Cu Catalysis4 Ru, Rh, and Ir Catalysis4.1 Alkenes4.2 1,3-Dienes4.3 Allenes4.4 Alkynes4.5 Enynes5 Fe, Co, and Mn Catalysis6 Conclusion and Outlook

Formic Acid Mediated Direct Z-Selective Reductive Coupling of Dienes and Aldehydes

2019 ◽  
Author(s):  
Christopher Cooze ◽  
Raphael Dada ◽  
Rylan Lundgren
Keyword(s):  
Formic Acid ◽  
Kinetic Analysis ◽  
Reductive Coupling ◽  
Ligand Dissociation ◽  
Rate Determining Step ◽  
Catalytically Active ◽  
Rapid Generation ◽  
Metal Catalyzed ◽  
Chain Walking

We demonstrate that formic acid mediates the Rh-catalyzed, Z-selective coupling of dienes and aldehydes. The process is distinguished by broad tolerance towards reducible or electrophilic groups. Kinetic analysis suggests that generation of the catalytically active Rh-intermediate by ligand dissociation is the rate determining step. The rapid generation and trapping of Rh-allyl intermediates is key to preventing chain-walking isomerization events that plague related protocols. Insights gained through this study may have wider implications in selective metal-catalyzed hydrofunctionalization reactions.<br>

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.

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