Methods Utilizing First-Row Transition Metals in Natural Product Total Synthesis

Zweig, Joshua E.; Kim, Daria E.; Newhouse, Timothy R.

doi:10.1021/acs.chemrev.6b00833

Cited by 188 publications

(74 citation statements)

References 856 publications

(1,060 reference statements)

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“…9,10 More importantly, copper shows excellent reactivity: Cu 0 , Cu I , Cu II , and Cu III oxidation states can be easily accessed, enabling radical pathways or two-electron bond formations. In addition to its redox properties, copper has the additional possibility of acting as a Lewis acid either through σ coordination to basic oxygen functionality or through π coordination with numerous functional groups.…”

Section: Introductionmentioning

confidence: 99%

Copper-Catalyzed Vinylogous Aerobic Oxidation of Unsaturated Compounds with Air

et al. 2018

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A mild and operationally simple copper-catalyzed vinylogous aerobic oxidation of β,γ- and α,β-unsaturated esters is described. This method features good yields, broad substrate scope, excellent chemo- and regioselectivity, and good functional group tolerance. This method is additionally capable of oxidizing β,γ- and α,β-unsaturated aldehydes, ketones, amides, nitriles, and sulfones. Furthermore, the present catalytic system is suitable for bisvinylogous and trisvinylogous oxidation. Tetramethylguanidine (TMG) was found to be crucial in its role as a base, but we also speculate that it serves as a ligand to copper(II) triflate to produce the active copper(II) catalyst. Mechanistic experiments conducted suggest a plausible reaction pathway via an allylcopper(II) species. Finally, the breadth of scope and power of this methodology are demonstrated through its application to complex natural product substrates.

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Section: Introductionmentioning

confidence: 99%

Copper-Catalyzed Vinylogous Aerobic Oxidation of Unsaturated Compounds with Air

et al. 2018

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“…Compared with noble transition metals (Pd, Ru, Rh, Ir, Pt), non‐noble transition metals, such as Fe, Co, and Ni, are attracting increasing attention in C−H activation because they are relatively earth‐abundant and less toxic . Notably, a perspective article on electrochemical cobalt‐catalyzed C−H bond activation has been published recently …”

Section: Anodic Cobalt‐catalyzed C−h Bond Functionalizationmentioning

confidence: 99%

Electrochemical Transition‐Metal‐Catalyzed C−H Bond Functionalization: Electricity as Clean Surrogates of Chemical Oxidants

Chen

Tian

2018

ChemSusChem

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Transition‐metal‐catalyzed C−H activation has attracted much attention from the organic synthetic community because it obviates the need to prefunctionalize substrates. However, superstoichiometric chemical oxidants, such as copper‐ or silver‐based metal oxidants, benzoquinones, organic peroxides, K2S2O8, hypervalent iodine, and O2, are required for most of the reactions. Thus, the development of environmentally benign and user‐friendly C−H bond activation protocols, in the absence of chemical oxidants, are urgently desired. The inherent advantages and unique characteristics of organic electrosynthesis make fill this gap. Herein, recent progress in this area (until the end of September 2018) is summarized for different transition metals to highlight the potential sustainability of electro‐organic chemistry.

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“…The insertion reactions of activated alkynes into the metal–hydride bond of metallocene hydride, especially the compounds containing Nb and Ta of group 5, continuously attract much attention, while studies on vananocenehydride have rarely been reported. In fact, the first‐row transition‐metal‐mediated reactions constitute an important and growing area of research owing to the low cost, low toxicity and exceptional synthetic versatility of these metals . The unique properties of first‐row transition metals, especially their generally reduced electronegativity, offer orthogonal opportunities for reaction development relative to their second‐ and third‐row counterparts.…”

Section: Introductionmentioning

confidence: 99%

Stereoselectivity and nonmigratory insertion mechanism of dimethylacetylene dicarboxylate into metallocene‐hydride of Cp₂M(L)H [Cp =η⁵‐C₅H₅; M = Nb, V; L = CO, P (OMe)₃]: A DFT study

Huo

Zeng

et al. 2020

Applied Organom Chemis

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The insertion of an alkyne into transition metal–hydrogen bonds is a key elementary step in catalytic polymerization and hydrogenation processes. It was found that a (Z)‐ or (E)‐type alkyenyl complex can be formed through trans/cis stereospecific processes. In this work, the reaction mechanism of Cp2M(L)H [Cp = η5‐C5H5; M = Nb, V; L = CO, P (OMe)3] with dimethylacetylene dicarboxylate (DMAD), and the factors influencing the stereoselectivity have been investigated based on density functional theory calculations. The calculated results show that all of the reactions are exothermic. For L = CO, the Z‐isomer product forms first even at low temperatures because of the low Gibbs free energy barrier (ΔG#). Then the Z‐pro converts to E‐pro, while for L = P (OMe)3, the exclusive product is the E‐isomer. For different metal centers, the reaction mechanisms of the Cp2M(CO)H + DMAD (M = Nb and V) reaction are similar, while their products are different at room temperature. For M = Nb, because the energy barrier of the isomerization from Z‐pro to E‐pro is low and the relative free energies of Z‐pro and E‐pro are almost equal, both Z‐pro and E‐pro can be obtained. While for the Cp2V(CO)H + DMAD reaction, only the Z‐pro can be obtained under mild conditions, E‐pro can be obtained only at high temperatures. For the Cp2M(CO)H+DMAD(M=V and Nb) reactions, the formation of E‐isomer products proceeds via two five‐membered ring transition states. The calculated results provide an reasonable explanation for the experimental results and predict a new insertion reaction.

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Methods Utilizing First-Row Transition Metals in Natural Product Total Synthesis

Cited by 188 publications

References 856 publications

Copper-Catalyzed Vinylogous Aerobic Oxidation of Unsaturated Compounds with Air

Copper-Catalyzed Vinylogous Aerobic Oxidation of Unsaturated Compounds with Air

Electrochemical Transition‐Metal‐Catalyzed C−H Bond Functionalization: Electricity as Clean Surrogates of Chemical Oxidants

Stereoselectivity and nonmigratory insertion mechanism of dimethylacetylene dicarboxylate into metallocene‐hydride of Cp₂M(L)H [Cp =η⁵‐C₅H₅; M = Nb, V; L = CO, P (OMe)₃]: A DFT study

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Methods Utilizing First-Row Transition Metals in Natural Product Total Synthesis

Cited by 188 publications

References 856 publications

Copper-Catalyzed Vinylogous Aerobic Oxidation of Unsaturated Compounds with Air

Copper-Catalyzed Vinylogous Aerobic Oxidation of Unsaturated Compounds with Air

Electrochemical Transition‐Metal‐Catalyzed C−H Bond Functionalization: Electricity as Clean Surrogates of Chemical Oxidants

Stereoselectivity and nonmigratory insertion mechanism of dimethylacetylene dicarboxylate into metallocene‐hydride of Cp2M(L)H [Cp =η5‐C5H5; M = Nb, V; L = CO, P (OMe)3]: A DFT study

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Stereoselectivity and nonmigratory insertion mechanism of dimethylacetylene dicarboxylate into metallocene‐hydride of Cp₂M(L)H [Cp =η⁵‐C₅H₅; M = Nb, V; L = CO, P (OMe)₃]: A DFT study