Not Just Heavy “Grignards”: Recent Advances in the Organometallic Chemistry of the Alkaline Earth Metals Calcium, Strontium and Barium

Alexander, Jacob S.; Ruhlandt‐Senge, Karin

doi:10.1002/1099-0682(200211)2002:11<2761::aid-ejic2761>3.0.co;2-2

Cited by 148 publications

(15 citation statements)

References 22 publications

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“…Over the past few decades, the understanding of the coordination chemistry of the elements of the heavy alkaline earth metals (M = Ca, Sr, Ba) has advanced dramatically, owing primarily to an interest in their application as chemical vapour deposition precursors (Hanusa 1990(Hanusa , 1993(Hanusa , 2000(Hanusa , 2002Westerhausen 1998Westerhausen , 2001Westerhausen , 2006Westerhausen , 2008Alexander & Ruhlandt-Senge 2002;Westerhausen et al 2007). Reaction studies upon organometallic compounds of calcium, strontium and barium have, however, been largely overshadowed by those of the lighter congener, magnesium.…”

Section: Introductionmentioning

confidence: 99%

Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium

et al. 2010

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Despite the routine employment of Grignard reagents and Hauser bases as stoichiometric carbanion reagents in organic and inorganic synthesis, a defined reaction chemistry encompassing the heavier elements of Group II (M = Ca, Sr and Ba) has, until recently, remained unreported. This article provides details of the recent progress in heavier Group II catalysed small molecule transformations mediated by well-defined heteroleptic and homoleptic complexes of the form LMX or MX 2 ; where L is a mono-anionic ligand and X is a reactive s-bonded substituent. The intra-and intermolecular heterofunctionalization (hydroamination, hydrophosphination, hydrosilylation and hydrogenation) of alkenes, alkynes, dienes, carbodiimides, isocyanates and ketones is discussed.

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Section: Introductionmentioning

confidence: 99%

Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium

et al. 2010

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“…Since then, organomagnesium compounds have greatly accelerated the advancement of synthetic chemistry and related subjects 1 . Nevertheless, the organometallic chemistry of heavy Grignard reagents (RAeX, Ae ¼ Ca, Sr and Ba) is still in its infancy due to the rather inert heavy alkalineearth metals and extremely high ionicity and reactivity of Ae-C bonds [2][3][4][5][6][7] . The enormous reactivity of generated Ae-C bonds easily led to side reactions and obstructed the application of heavy Grignard reagents [8][9][10][11][12] .…”

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Intramolecular C–F and C–H bond cleavage promoted by butadienyl heavy Grignard reagents

Wang

Wei

et al. 2014

Nat Commun

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Organomagnesium compounds (Grignard reagents) are among the most useful organometallic reagents and have greatly accelerated the advancement of synthetic chemistry and related sciences. Nevertheless, heavy Grignard reagents based on the metals calcium, strontium or barium are not widely used, mainly due to their rather inert heavy alkaline-earth metals and extremely high reactivity of their corresponding Grignard-type reagents. Here we report the generation and reaction chemistry of butadienyl heavy Grignard reagents whose extremely high reactivity is successfully tamed. Facile synthesis of perfluoro-π-extended pentalene and naphthalene derivatives is realized by the in situ generated heavy Grignard reagents via intramolecular C-F/C-H bond cleavage. These obtained perfluorodibenzopentalene and perfluorodinaphthopentalene derivatives show low-lying LUMO levels, with one being the lowest value so far among all pentalene derivatives. Our results set an exciting example for the meaningful synthetic application of heavy Grignard reagents.

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“…On green chemistry perspective, the use of alkaline earth metals in organic reactions are favorable due to the fact that, metals such as calcium and magnesium are ubiquitously available in nature compared to other transition and lanthanide elements [15]. However, only limited organic reactions which employ alkaline earth metals as catalysts were reported as their applications are not being fully explored [16].…”

Section: -2506mentioning

confidence: 99%

MgCl2 AS EFFICIENT AND INEXPENSIVE CATALYST FOR THE SYNTHESIS OF 1,4-DIHYDROPYRIDINE DERIVATIVES

2017

MJAS

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The synthesis of 1,4-dihydropyridine (1,4-DHP) derivatives in the presence of alkaline earth metal chlorides was reported. Specifically, the MgCl 2 catalyzed the synthesis of 1,4-DHP derivatives in good yields, ranging from 69 -87%. The Mg 2+ serves as the Lewis acid catalyst in the formation of 1,4-DHP and the proposed mechanism of the formation of 1,4-DHP was elaborated in this manuscript. There are many advantages employing MgCl 2 as a catalyst in this study, including inexpensive, ubiquitous availability of this metal, simple filtration protocol, which has spark considerable interest in the use of this catalyst in promoting organic reactions.Keywords: alkaline earth metal, magnesium chloride; 1,4-dihydropyridine Abstrak Sintesis terbitan 1,4-dihidropiridina (1,4-DHP) dalam kehadiran logam alkali bumi dibincangkan dalam artikel ini. Secara khususnya, sintesis terbitan 1,4-DHP melalui pemangkin MgCl 2 memberi peratusan hasil yang baik, dalam lingkungan 69 -87%. Ion Mg 2+ bertindak sebagai pemangkin asid Lewis dalam pembentukan 1,4-DHP dan cadangan mekanisma terhadap pembentukan 1,4-DHP telah dihuraikan dalam manuskrip ini. Terdapat banyak kelebihan menggunakan MgCl 2 sebagai pemangkin dalam kajian ini, termasuk kos yang murah, ketersediaan logam ini, protokol pengekstrakan yang mudah, yang mana ini telah mencetuskan minat yang besar dalam penggunaan pemangkin ini dalam pelbagai tindak balas organik.Kata kunci: logam alkali bumi, magnesium klorida, 1,4-dihydropiridin Introduction 1,4-dihydropyrdines (1,4-DHPs) are important classes of pharmaceutical compounds that are usually prescribed clinically for the treatment of cardiovascular diseases, such as heart failure, angina pectoris and hypertension [1]. In the pharmaceutical pipeline today, there are more than twelve 1,4-DHPs drug candidates commercially available in the global market, such as the nifedipine [2], felodipine [3], nicardipine [4] and etc., which were used to treat cardiovascular diseases.

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Not Just Heavy “Grignards”: Recent Advances in the Organometallic Chemistry of the Alkaline Earth Metals Calcium, Strontium and Barium

Cited by 148 publications

References 22 publications

Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium

Heterofunctionalization catalysis with organometallic complexes of calcium, strontium and barium

Intramolecular C–F and C–H bond cleavage promoted by butadienyl heavy Grignard reagents

MgCl2 AS EFFICIENT AND INEXPENSIVE CATALYST FOR THE SYNTHESIS OF 1,4-DIHYDROPYRIDINE DERIVATIVES

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