Reactivity of [TismPriBenz]MgH and [TismPriBenz]MgMe Towards Esters: Alkoxide Elimination and C–C Bond Formation

IF 2.9 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2025-08-26 DOI:10.1021/acs.organomet.5c00190

David A. Vaccaro, Ran Yan and Gerard Parkin*,

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Abstract

The reactivity of Mg–H and Mg–Me bonds of [Tism^PrⁱBenz]MgH and [Tism^PrⁱBenz]MgMe towards esters reveals additional pathways to those that have been observed for aldehydes and ketones, namely insertion and enolate formation. For example, [Tism^PrⁱBenz]MgH and [Tism^PrⁱBenz]MgMe react with the formate ester HCO₂Me to afford the methoxy derivative, [Tism^PrⁱBenz]MgOMe, via a process that is proposed to involve β-methoxide elimination from a [Tism^PrⁱBenz]MgOCH(X)OMe intermediate (X = H, Me). Likewise, [Tism^PrⁱBenz]MgH reacts with the acetate ester, MeCO₂Et, to afford the ethoxide complex, [Tism^PrⁱBenz]MgOEt. In contrast, while the methyl complex [Tism^PrⁱBenz]MgMe likewise reacts with MeCO₂Et to form [Tism^PrⁱBenz]MgOEt, the β-keto ester enolate derivative, [Tism^PrⁱBenz]Mg(κ²-etac) [κ²-etac = MeC(O)CHC(O)OEt], is also obtained via a reaction that involves the formation of a C–C bond. The latter compound is additionally obtained by the reaction of [Tism^PrⁱBenz]MgMe with ethyl acetoacetate, MeC(O)CH₂C(O)OEt, presumably via a reaction with the enol tautomer, MeC(OH)CHC(O)OEt. [Tism^PrⁱBenz]MgOMe and [Tism^PrⁱBenz]Mg(κ²-etac) have been structurally characterized by X-ray diffraction.

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[TismPriBenz]MgH和[TismPriBenz]MgMe对酯的反应性：醇酮消除和C-C键形成

[TismPriBenz]MgH和[TismPriBenz]MgMe的Mg-H和Mg-Me键对酯的反应性揭示了与已观察到的醛和酮的其他途径，即插入和烯酸酯形成。例如，[TismPriBenz]MgH和[TismPriBenz]MgMe与甲酸酯HCO2Me反应生成甲氧基衍生物[TismPriBenz]MgOCH(X)OMe中间体（X = H, Me）的β-甲氧基消除过程。同样，[TismPriBenz]MgH与乙酸酯MeCO2Et反应，生成[TismPriBenz]MgOEt乙氧化物配合物。相反，甲基配合物[TismPriBenz]MgMe同样与MeCO2Et反应生成[TismPriBenz]MgOEt， β-酮酯烯酸酯衍生物[TismPriBenz]Mg(κ2-etac) [κ2-etac = MeC(O)CHC(O)OEt]也通过涉及形成C-C键的反应得到。后一种化合物是由[tissmpribenz]MgMe与乙酰乙酸乙酯MeC(O)CH2C(O)OEt反应得到的，可能是通过与烯醇互变异构体MeC(OH)CHC(O)OEt反应得到的。用x射线衍射对[TismPriBenz] mome和[TismPriBenz]Mg（κ2-etac）进行了结构表征。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.