ESI-MS, DFT, and Synthetic Studies on the H2-Mediated Coupling of Acetylene: Insertion of C═X Bonds into Rhodacyclopentadienes and Brønsted Acid Cocatalyzed Hydrogenolysis of Org

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• 作者：Vanessa M. Williams ; Jong Rock Kong ; Byoung Joon Ko ; Yogita Mantri ; Jennifer S. Brodbelt ; Mu-Hyun Baik ; Michael J. Krische
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：November 11, 2009
• 年：2009
• 卷：131
• 期：44
• 页码：16054-16062
• 全文大小：373K
• 年卷期：v.131,no.44(November 11, 2009)
• ISSN：1520-5126

文摘

The catalytic mechanism of the hydrogen-mediated coupling of acetylene to carbonyl compounds and imines has been examined using three techniques: (a) ESI-MS and ESI-CAD-MS analyses, (b) computational modeling, and (c) experiments wherein putative reactive intermediates are diverted to alternate reaction products. ESI-MS analysis of reaction mixtures from the hydrogen-mediated reductive coupling of acetylene to α-ketoesters or N-benzenesulfonyl aldimines corroborate a catalytic mechanism involving C═X (X = O, NSO₂Ph) insertion into a cationic rhodacyclopentadiene obtained by way of acetylene oxidative dimerization with subsequent Brønsted acid cocatalyzed hydrogenolysis of the resulting oxa- or azarhodacycloheptadiene. Hydrogenation of 1,6-diynes in the presence of α-ketoesters provides analogous coupling products. ESI mass spectrometric analysis again corroborates a catalytic mechanism involving carbonyl insertion into a cationic rhodacyclopentadiene. For all ESI-MS experiments, the structural assignments of ions are supported by multistage collisional activated dissociation (CAD) analyses. Further support for the proposed catalytic mechanism derives from experiments aimed at the interception of putative reactive intermediates and their diversion to alternate reaction products. For example, rhodium-catalyzed coupling of acetylene to an aldehyde in the absence of hydrogen or Brønsted acid cocatalyst provides the corresponding (Z)-butadienyl ketone, which arises from β-hydride elimination of the proposed oxarhodacycloheptadiene intermediate, as corroborated by isotopic labeling. Additionally, the putative rhodacyclopentadiene intermediate obtained from the oxidative coupling of acetylene is diverted to the product of reductive [2 + 2 + 2] cycloaddition when N-p-toluenesulfonyl-dehydroalanine ethyl ester is used as the coupling partner. The mechanism of this transformation also is corroborated by isotopic labeling. Computer model studies based on density functional theory (DFT) support the proposed mechanism and identify Brønsted acid cocatalyst assisted hydrogenolysis to be the most difficult step. The collective studies provide new insight into the reactivity of cationic rhodacyclopentadienes, which should facilitate the design of related rhodium-catalyzed C−C couplings.