Organoiron and Organochromium Chemistry

Semmelhack, M. F.

doi:10.1002/9781118750421.ch9

Cited by 3 publications

(4 citation statements)

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“…The η 1 -alkyltetracarbonylferrate(0), coming from the reaction with an alkylating agent, undergoes a migratory insertion to produce an η 1 -acyltricarbonylferrate(0). Subsequent reaction with an electrophile occurs through oxidative addition/reductive elimination (Scheme ). , …”

Section: Reactions Of Maas Involving Nucleophile Ligand Transfer Proc...mentioning

confidence: 99%

Mixed AggregAte (MAA): A Single Concept for All Dipolar Organometallic Aggregates. 2. Syntheses and Reactivities of Homo/HeteroMAAs

2013

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6. Conclusion 7706 Author Information 7706 Biographies 7707 Acknowledgment 7707 Abbreviations Used 7707 References 7708the corresponding allyl-and propargylchromium reagents that further react with a variety of electrophiles to afford the corresponding adducts in high yields. 102 Bu 6 CrLi 3 similarly behaves as a formal two-electron reductant with ketones and esters bearing a leaving group at the α-position to produce enolates that are intercepted with a variety of electrophiles with high selectivities (Table 8). 103 Such enolates are also capable of reacting with oxiranes to afford γand β-hydroxy esters, depending on the Lewis acid used as promoter. 2143.2.2. Two-Electron Transfers from M,Mn-HeteroMAAs (M = Li, MgX). In 1976, Cahiez et al. disclosed the possible reduction in THF of alkenyl bromides or iodides, as well as aryl chlorides or bromides, using i-PrMgCl in the presence of a catalytic amount of MnCl 2 . 215 The authors proposed the in situ formation of unstable i-Pr 3 MnMgCl and its decomposition by β-elimination to H 3 MnMgCl; reaction of the latter with the halide would then afford an unstable Mn(IV) intermediate, able Scheme 23 Scheme 24 Scheme 21 Scheme 22

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Section: Reactions Of Maas Involving Nucleophile Ligand Transfer Proc...mentioning

confidence: 99%

Mixed AggregAte (MAA): A Single Concept for All Dipolar Organometallic Aggregates. 2. Syntheses and Reactivities of Homo/HeteroMAAs

2013

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“…To this end, we resorted to the preparation and study of fairly stable tricarbonyliron complexes . The strong ligand field of CO renders such Fe(0) complexes diamagnetic.…”

Section: Results and Discussonmentioning

confidence: 99%

“…The mechanism of this transformation, which has hardly any precedent in the literature, , awaits experimental scrutiny. The reaction might commence with π-complex formation ( B ) with the (loaded) iron catalyst followed by a formal 1,6-addition reaction (Scheme ). The resulting enolate C presumably undergoes an electrocyclic ring opening, although the reasons for the high torquoselectivity as necessary for the exclusive formation of dienoate D are not intuitive.…”

Section: Introductionmentioning

confidence: 99%

Catalysis-Based Total Syntheses of Pateamine A and DMDA-Pat A

Zhuo

Fürstner

2018

J. Am. Chem. Soc.

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The marine natural product pateamine A (1) and its somewhat simplified designer analogue DMDA-Pat A (2) (DMDA = desmethyl-desamino) are potently cytotoxic compounds; most notably, 2 had previously been found to exhibit a promising differential in vivo activity in xenograft melanoma models, even though the ubiquitous eukaryotic initiation factor 4A (eIF4A) constitutes its primary biological target. In addition, 1 had also been identified as a possible lead in the quest for medication against cachexia, an often lethal muscle wasting syndrome affecting many immunocompromised or cancer patients. The short supply of these macrodiolides, however, rendered a more detailed biological assessment difficult. Therefore, a new synthetic approach to 1 and 2 has been devised, which centers on an unorthodox strategy for the formation of the highly isomerization-prone but essential Z, E-configured dienoate substructure embedded into the macrocyclic core. This motif was encoded in the form of a 2-pyrone ring and unveiled only immediately before macrocyclization by an unconventional iron-catalyzed ring opening/cross-coupling reaction, in which the enol ester entity of the pyrone gains the role of a leaving group. Since the required precursor was readily available by gold catalysis, this strategy rendered the overall sequence short, robust, and scalable. A surprisingly easy protecting group management together with a much improved end game for the formation of the trienyl side chain via a modern Stille coupling protocol also helped to make the chosen route practical. Change of a single building block allowed the synthesis to be redirected from the natural lead compound 1 toward its almost equipotent analogue 2. Isolation and reactivity profiling of pyrone tricarbonyliron complexes provide mechanistic information as well as insights into the likely origins of the observed chemoselectivity.

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“…Li 2 [Fe(C 2 H 4 ) 4 ], which was prepared by Jonas and Schieferstein [25], afforded the cross-coupling reaction with comparatively high rates and yields (Scheme 5.9). This observation is of particular interest in the context that the highly nucleophilic Na 2 Fe(CO) 4 [ formally Fe(ÀII)] developed by Collman [26] did not pursue the cross-coupling reaction under the reported conditions. …”

Section: Cross-coupling Reactions Of Aryl Electrophilesmentioning

confidence: 93%

Iron‐Catalyzed Cross‐Coupling Reactions

Leitner¹

2008

Iron Catalysis in Organic Chemistry

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Organoiron and Organochromium Chemistry

Cited by 3 publications

References 225 publications

Mixed AggregAte (MAA): A Single Concept for All Dipolar Organometallic Aggregates. 2. Syntheses and Reactivities of Homo/HeteroMAAs

Mixed AggregAte (MAA): A Single Concept for All Dipolar Organometallic Aggregates. 2. Syntheses and Reactivities of Homo/HeteroMAAs

Catalysis-Based Total Syntheses of Pateamine A and DMDA-Pat A

Iron‐Catalyzed Cross‐Coupling Reactions

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