Iron-catalyzed protodehalogenation of alkyl and aryl halides using hydrosilanes

Pilli, Ramadevi; Balakrishnan, Venkadesh; Chandrasekaran, Revathi; Rasappan, Ramesh

doi:10.1039/c8ob02365d

Cited by 13 publications

(3 citation statements)

References 39 publications

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“…In particular, the tolerance of this catalytic system toward primary chlorides must be underscored since this functional group can undergo reduction to the alkane stage in the presence of silanes and iron catalysts. 44 Cyclohexyl substituted vinylsilane 3la (99% yield) was obtained with a 15:85 selectivity for the β regioisomer, but cyclopropyl vinylsilane 3ma (91%) was obtained with a slight bias toward the α isomer (α/β = 58:42). This intriguing divergence in regioselectivity might be attributed to the high sp 2 character of the cyclopropyl motif or to a lowered steric hindrance.…”

Section: ■ Results and Discussionmentioning

confidence: 98%

“…Noteworthily, handles for functionalization such as alkene ( 3ja ) and primary chloride ( 3ka ) remained untouched under the reaction conditions, showcasing the selectivity of this protocol. In particular, the tolerance of this catalytic system toward primary chlorides must be underscored since this functional group can undergo reduction to the alkane stage in the presence of silanes and iron catalysts . Cyclohexyl substituted vinylsilane 3la (99% yield) was obtained with a 15:85 selectivity for the β regioisomer, but cyclopropyl vinylsilane 3ma (91%) was obtained with a slight bias toward the α isomer (α/β = 58:42).…”

Section: Resultsmentioning

confidence: 99%

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Cation-Assisted Hydrosilylation of Alkynes Catalyzed by a Low-Valent Iron Complex Bearing Noninnocent Ligands

G.-Simonian,

Féo,

Tanguy

et al. 2024

ACS Catal.

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The field of iron catalysis often faces hurdles in accommodating its transient and unstable low-valent intermediates. By harnessing the noninnocent character of commercial bathocuproine ligand, we managed to develop a reliable functionalization of alkynes with primary, secondary, and tertiary silanes but also with germanium hydrides, catalyzed by a low-valent iron complex. The robustness of the catalyst enabled gram-scale synthesis of vinylsilanes, low catalytic loading, one-pot, hetero, bis-hydrosilylation, but also high steric build-up. Mechanistic studies suggest an important effect of the Mg II cation resulting from the reduction of the precatalyst, by assisting the dynamic generation of a highly reactive, under-coordinated iron species from a stable complex.

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Section: ■ Results and Discussionmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Cation-Assisted Hydrosilylation of Alkynes Catalyzed by a Low-Valent Iron Complex Bearing Noninnocent Ligands

G.-Simonian,

Féo,

Tanguy

et al. 2024

ACS Catal.

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“…We were also attracted towards the use of 1,4‐cyclohexadiene (CHD) as the source of hydrogen atom since the resultant benzene could easily be removed, thus simplifying the purification process. As part of our ongoing interest in field of iron mediated catalytic reactions, we present here an iron mediated reduction and cyclization of alkyl halides.…”

Section: Methodsmentioning

confidence: 96%

A Free‐Radical Reduction and Cyclization of Alkyl Halides Mediated by FeCl₂

et al. 2019

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Iron mediated catalytic reactions are of great interest in the field of organic synthesis because they are economic and naturally abundant. However, the use of iron catalyst in the field of free radical cyclization or reduction of alkyl halides remains limited. Here we describe the use of an unprecedented combination of iron and zinc in the reduction and 5‐exo‐trig radical cyclization of alkyl halides under mild condition in the absence of added ligands or additives. The method is distinguished by its wide scope, functional group tolerance and the use of 1,4‐cyclohexadiene as the source of hydrogen, which aids easy purification.

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Oxidation and Reduction

Mehrotra¹

2023

Organic Reaction Mechanisms Series

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Iron-catalyzed protodehalogenation of alkyl and aryl halides using hydrosilanes

Abstract: A simple and efficient iron-catalyzed protodehalogenation of alkyl and aryl halides using phenylhydrosilane is disclosed.

Cited by 13 publications

References 39 publications

Cation-Assisted Hydrosilylation of Alkynes Catalyzed by a Low-Valent Iron Complex Bearing Noninnocent Ligands

Cation-Assisted Hydrosilylation of Alkynes Catalyzed by a Low-Valent Iron Complex Bearing Noninnocent Ligands

A Free‐Radical Reduction and Cyclization of Alkyl Halides Mediated by FeCl₂

Oxidation and Reduction

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Iron-catalyzed protodehalogenation of alkyl and aryl halides using hydrosilanes

Abstract: A simple and efficient iron-catalyzed protodehalogenation of alkyl and aryl halides using phenylhydrosilane is disclosed.

Cited by 13 publications

References 39 publications

Cation-Assisted Hydrosilylation of Alkynes Catalyzed by a Low-Valent Iron Complex Bearing Noninnocent Ligands

Cation-Assisted Hydrosilylation of Alkynes Catalyzed by a Low-Valent Iron Complex Bearing Noninnocent Ligands

A Free‐Radical Reduction and Cyclization of Alkyl Halides Mediated by FeCl2

Oxidation and Reduction

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A Free‐Radical Reduction and Cyclization of Alkyl Halides Mediated by FeCl₂