Synthesis and Reactivity of Organometallic Intermediates Relevant to Cobalt-Catalyzed Hydroformylation.,Angewandte Chemie International Edition

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Synthesis and Reactivity of Organometallic Intermediates Relevant to Cobalt-Catalyzed Hydroformylation.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-03-17 , DOI: 10.1002/anie.202001677
Connor S MacNeil ₁ , Lauren N Mendelsohn ₁ , Hongyu Zhong ₁ , Tyler P Pabst ₁ , Paul J Chirik ₁

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Intermediates relevant to cobalt-catalyzed alkene hydroformylation have been isolated and evaluated in fundamental organometallic transformations relevant to aldehyde formation. The 18-electron (R,R)-(iPr DuPhos)Co(CO)2 H has been structurally characterized, and it promotes exclusive hydrogenation of styrene in the presence of 50 bar of H2 /CO gas (1:1) at 100 °C. Deuterium-labeling studies established reversible 2,1-insertion of styrene into the Co-D bond of (R,R)-(iPr DuPhos)Co(CO)2 D. Whereas rapid β-hydrogen elimination from cobalt alkyls occurred under an N2 atmosphere, alkylation of (R,R)-(iPr DuPhos)Co(CO)2 Cl in the presence of CO enabled the interception of (R,R)-(iPr DuPhos)Co(CO)2 C(O)CH2 CH2 Ph, which upon hydrogenolysis under 4 atm H2 produced the corresponding aldehyde and cobalt hydride, demonstrating the feasibility of elementary steps in hydroformylation. Both the hydride and chloride derivatives, (X=H- , Cl- ), underwent exchange with free 13 CO. Under reduced pressure, (R,R)-(iPr DuPhos)Co(CO)2 Cl underwent CO dissociation to form (R,R)-(iPr DuPhos)Co(CO)Cl.

中文翻译：

与钴催化的加氢甲酰化反应有关的有机金属中间体的合成和反应性。

与钴催化的烯烃加氢甲酰化有关的中间体已被分离出来，并在与醛形成有关的基本有机金属转化中进行了评估。18电子（R，R）-（iPr DuPhos）Co（CO）2 H具有结构特征，在50 bar的H2 / CO气体（1：1）和100 bar的氢气存在下可促进苯乙烯的独家氢化℃。氘标记研究确定了将苯乙烯可逆地2,1-插入到（R，R）-（iPr DuPhos）Co（CO）2 D的Co-D键中。而在N2下，从钴烷基中快速去除β-氢大气中，在CO存在下（R，R）-（iPr DuPhos）Co（CO）2 Cl的烷基化使得能够截获（R，R）-（iPr DuPhos）Co（CO）2 C（O）CH2 CH2 Ph，在4 atm H2下氢解后产生相应的醛和氢化钴，证明了加氢甲酰化基本步骤的可行性。氢化物和氯化物衍生物（X = H-，Cl-）均与游离的13 CO交换。在减压下，（R，R）-（iPr DuPhos）Co（CO）2 Cl经历CO离解形成（ R，R）-（iPr DuPhos）Co（CO）Cl。

更新日期：2020-03-17

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