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Journal ArticleDOI

Iron Porphyrin Catalyzed N−H Insertion Reactions with Ethyl Diazoacetate

04 Jul 2007-Organometallics (American Chemical Society)-Vol. 26, Iss: 16, pp 3995-4002
TL;DR: In this article, a series of metalloporphyrin complexes were surveyed as catalysts for carbene insertion from ethyl diazoacetate into the N−H bonds of amines.
About: This article is published in Organometallics.The article was published on 2007-07-04 and is currently open access. It has received 98 citations till now. The article focuses on the topics: Ethyl diazoacetate & Insertion reaction.
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TL;DR: This work aims to demonstrate the efforts towards in-situ applicability of EMMARM, which aims to provide real-time information about the physical properties of EMTs and their applications in the context of drug discovery and development.
Abstract: Alan Ford,† Hugues Miel, Aoife Ring,† Catherine N. Slattery,† Anita R. Maguire,*,†,‡ and M. Anthony McKervey* †Department of Chemistry and ‡School of Pharmacy, Analytical and Biological Chemistry Research Facility, Synthesis and Solid State Pharmaceutical Centre, University College Cork, Cork, Ireland Almac Discovery Ltd., David Keir Building, Stranmillis Road, Belfast BT9 5AG, United Kingdom Almac Sciences Ltd., Almac House, 20 Seagoe Industrial Estate, Craigavon BT63 5QD, United Kingdom

1,051 citations

Journal ArticleDOI
TL;DR: The following review will explore the historical development of X-H insertion and give an up-to-date account of the metal catalysts most often employed, including an assessment of their strengths and weaknesses.
Abstract: Catalysed X–H insertion reactions into diazo compounds (where X is any heteroatom) are a powerful yet underutilized class of transformations. The following review will explore the historical development of X–H insertion and give an up-to-date account of the metal catalysts most often employed, including an assessment of their strengths and weaknesses. Despite decades of development, recent work on enantioselective variants, as well as applying catalytic X–H insertion towards problems in chemical biology indicate that this field has ample room for innovation.

394 citations

Journal ArticleDOI
TL;DR: This work demonstrates enzyme-catalyzed insertion of carbenoids into N-H bonds, which has no counterpart in nature, and can be mediated by variants of the cytochrome P450 from Bacillus megaterium.
Abstract: Expanding nature's catalytic repertoire to include reactions important in synthetic chemistry will open new opportunities for ‘green’ chemistry and biosynthesis. We demonstrate the first enzyme-catalyzed insertion of carbenoids into N–H bonds. This type of bond disconnection, which has no counterpart in nature, can be mediated by variants of the cytochrome P450 from Bacillus megaterium. The N–H insertion reaction takes place in water, provides the desired products in 26–83% yield, forms the single addition product exclusively, and does not require slow addition of the diazo component.

139 citations

Journal ArticleDOI
TL;DR: The field of iron catalysis has been explored in the last two-three decades out of its rich chemistry depending on its oxidation states and ligand cooperation as discussed by the authors, and this field has been enriched by the promising development of iron-catalyzed reactions namely, C-H bond activation, including organometallic C−H activation and C−h functionalization via outer-sphere pathway, crossdehydrogenative couplings, insertion reactions, cross-coupling reactions, hydrogenations including hydrogen borrowing reactions, hydrosilylation and hydroboration, addition reactions
Abstract: In industries and academic laboratories, several late transition metal-catalyzed prerequisite reactions are widely performed during single and multistep synthesis. However, besides the desired products, these reactions lead to the generation of numerous chemical waste materials, by-products, hazardous gases, and other poisonous materials, which are discarded in the environment. This is partly responsible for the creation of global warming, resulting in climate adversities. Thus, the development of environmentally benign, cheap, easily accessible, and earth-abundant metal catalysts is desirable to minimize these issues. Certainly, iron is one of the most important metals belonging to this family. The field of iron catalysis has been explored in the last two-three decades out of its rich chemistry depending on its oxidation states and ligand cooperation. Moreover, this field has been enriched by the promising development of iron-catalyzed reactions namely, C–H bond activation, including organometallic C–H activation and C–H functionalization via outer-sphere pathway, cross-dehydrogenative couplings, insertion reactions, cross-coupling reactions, hydrogenations including hydrogen borrowing reactions, hydrosilylation and hydroboration, addition reactions and substitution reactions. Thus, herein an inclusive overview of these reaction have been well documented.

128 citations

References
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Journal ArticleDOI
TL;DR: Epoxydation asymetrique d'olefines prochirales par des porphyrines de fer chirales and par des composes iodosyles.
Abstract: Epoxydation asymetrique d'olefines prochirales par des porphyrines de fer chirales et par des composes iodosyles

416 citations

Journal ArticleDOI
TL;DR: Rhodium carbenoids derived from methyl aryldiazoacetates are capable of effective catalytic asymmetric C−H activation of a range of alkanes and tetrahydrofuran by a c−H insertion mechanism as mentioned in this paper.
Abstract: Rhodium carbenoids derived from methyl aryldiazoacetates are capable of effective catalytic asymmetric C−H activation of a range of alkanes and tetrahydrofuran by a C−H insertion mechanism. Dirhodium tetrakis(S-(N-dodecylbenzenesulfonyl)prolinate) (Rh2(S-DOSP)4) catalyzed decomposition of methyl aryldiazoacetates in the presence of alkanes results in intermolecular C−H insertions with good control of regioselectivity, diastereoselectivity, and enantioselectivity. The carbenoids derived from methyl aryldiazoacetates are considerably more chemoselective than carbenoids derived from diazoacetates. They strongly favor C−H insertions into secondary and tertiary sites. Formation of side products due to carbene dimerization is not a major problem with rhodium carbenoids derived from aryldiazoacetates.

296 citations