Dearomatized BIAN Alkaline-Earth Alkyl Catalysts for the Intramolecular Hydroamination of Hindered Aminoalkenes

Arrowsmith, Merle; Hill, Michael S.; Kociok‐Köhn, Gabriele

doi:10.1021/om400955v

Cited by 41 publications

(33 citation statements)

References 78 publications

(70 reference statements)

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“…[14] By changingt he chelate ring size from six-membered to fivemembered, catalyst 8 has higher catalytic activity than 1 while maintaining the stabilityt oward Schlenk-type rearrangements. [14] By changingt he chelate ring size from six-membered to fivemembered, catalyst 8 has higher catalytic activity than 1 while maintaining the stabilityt oward Schlenk-type rearrangements.…”

Section: Hydroaminationmentioning

confidence: 99%

“…In contrast, if complex 10 is applied to the catalytic hydroboration of pyridines, the regioselectivity is not translatedf rom the Scheme7.The Hill catalyst 8 and as elected hydroamination reaction. [17] ChemCatChem 2016, 8, [10][11][12][13][14][15][16][17][18][19][20] www.chemcatchem.org stoichiometric reaction. [15] Scheme9.Proposed catalytic cycle for the magnesium-catalyzedhydroboration of pyridines.…”

Section: Hydroborationmentioning

confidence: 99%

“…[24] In this reaction,t he active catalyst, am agnesium hydridoboratec omplex (1e), wasp re-Scheme10. [21] ChemCatChem 2016, 8, [10][11][12][13][14][15][16][17][18][19][20] www.chemcatchem.org pared either from hydride complex 1c or an aminoborane complex (similar to the one shown in Scheme 19) by addition of B(C 6 F 5 ) 3 .C atalyst 1e was effective in transforming CO 2 with three equivalents of pinacol borate to the methanol borate and the diboroxane (Scheme13). [20] Scheme11.…”

Section: Hydroborationmentioning

confidence: 99%

“…[23] Scheme13. [26] ChemCatChem 2016, 8, [10][11][12][13][14][15][16][17][18][19][20] www.chemcatchem.org [24] Scheme14.…”

Section: Hydrosilylationunclassified

“…The nitrogen atom of the initially generated amidomagnesium complex attacks the silicon center in the rate-determining step to form ap entacoordinated silicon in the coordination sphere of magnesium. [30] ChemCatChem 2016, 8, [10][11][12][13][14][15][16][17][18][19][20] www.chemcatchem.org dride is transferred to magnesiuma nd the silane amine is released, yielding am agnesium hydride complex. Mechanism proposed by Harder and co-workers for their dehydrocoupling of aminoboranes.…”

Section: Dehydrocoupling Of Silanes and Aminesmentioning

confidence: 99%

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Recent Developments in Homogeneous Organomagnesium Catalysis

et al. 2015

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Stoichiometric organomagnesium chemistry has continually progressed since its initiation by Victor Grignard over one century ago. Other than acting as a Lewis acid, however, homogeneous magnesium catalysis is a rare topic in the literature. Magnesium catalysts that govern reactions within the coordination sphere of magnesium have only recently begun to appear. This Concept covers recent progress in this young but potentially powerful new chapter of magnesium chemistry.

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Section: Hydroaminationmentioning

confidence: 99%

Section: Hydroborationmentioning

confidence: 99%

Section: Hydroborationmentioning

confidence: 99%

“…[23] Scheme13. [26] ChemCatChem 2016, 8, [10][11][12][13][14][15][16][17][18][19][20] www.chemcatchem.org [24] Scheme14.…”

Section: Hydrosilylationunclassified

Section: Dehydrocoupling Of Silanes and Aminesmentioning

confidence: 99%

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Recent Developments in Homogeneous Organomagnesium Catalysis

et al. 2015

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Hydroamination of Alkenes

Reznichenko

Hultzsch

2015

Organic Reactions

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The addition of an amine NH‐functionality to alkenes (including vinyl arenes, conjugated dienes, allenes or ring‐strained alkenes), the so‐called hydroamination, represents a simple and highly atom‐economical approach for the synthesis of nitrogen‐containing products. A large variety of catalyst systems are available, ranging from alkali, alkaline earth, rare earth, Group 4 and Group 5 metals, to late transition metal catalysts, and, less prominent, Brønsted and Lewis acid‐based catalyst systems. The mode of operation of these catalyst systems can vary significantly and the different reaction mechanisms and the scope and limitations are discussed. While intramolecular hydroamination reactions can be readily achieved with a large number of catalyst systems, significantly fewer examples for the more challenging intermolecular hydroamination are known, especially for unactivated alkenes. The stereoselective hydroamination has also received significant attention due to the importance of chiral nitrogen‐containing molecules in pharmaceutical industry. A variety of highly selective chiral catalyst systems have been developed for intramolecular hydroaminations, while examples of intermolecular asymmetric hydroaminations are scarce. Hydroamination in the context of this review article is defined as the addition of HNR 2 across a non‐activated, unsaturated carbon‐carbon multiple bond. This review focuses on the hydroamination reaction of simple, non‐activated alkenes. The addition of amines to slightly activated alkenes, such as vinyl arenes, 1,3‐dienes, strained alkenes (norbornene derivatives, methylenecyclopropenes) and allenes is closely related and is covered as well. However, hydroamination reactions of alkynes and Aza‐Michael reactions involving the addition of an N‐H fragment across the conjugated or otherwise activated double bond of a Michael acceptor are not covered. The scope of amine types includes ammonia, primary and secondary aliphatic and aromatic amines, azoles, and hydrazines. N ‐Protected amines, such as ureas, carboxamides, and sulfonamides are covered as well, as they are important substrates for metal‐free and late transition metal‐based catalysts. The literature through January 2011 will be covered with two selected references from 2012 (comprising Table 3D). A supplemental reference list is provided for reports appearing February 2011 through April 2015. The chapter is organized by the nature of the carbon unsaturation to which the amine is added. Ranging from less reactive substrates such as ethylene and unactivated alkenes, to slightly activated substrates, such as vinyl arenes, and more activated substrates, including conjugated dienes, allenes and strained alkenes. Enantioselective hydroamination reactions, an area that has seen significant progress over the past decade, are discussed next. Finally, tandem hydroamination/carbocyclization reactions of aminodialkenes provide rapid access to complex alkaloidal skeletons. The tables at the end of the chapter are separated into five main sections: achiral intermolecular hydroamination, achiral intramolecular hydroamination, enantioselective intermolecular hydroamination, enantioselective intramolecular hydroamination, and tandem hydroamination/carbocyclization. Within the first four sections the tables are further divided into subsections based on the participating alkene, i.e. alkenes, vinyl arenes, dienes, allenes, and strained alkenes.

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Magnesium and Calcium Complexes in Homogeneous Catalysis

Arrowsmith

2015

Encyclopedia of Inorganic and Bioinorganic Chemistry

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This article provides an overview of recent progress in homogeneous catalysis using organometallic complexes of the earth‐abundant and biocompatible elements, magnesium and calcium. It is divided into polymerization of activated monomers, heterofunctionalization of polar unsaturated substrates, and dehydrocoupling catalyses. As the subject of lighter alkaline earth‐catalyzed polymerization reactions is too broad to fully cover herein, the focus remains on anionic styrene polymerization and the ring‐opening polymerization of lactide. Dimerization reactions of aldehydes and terminal acetylenes are also briefly described. Heterofunctionalization reactions include catalyses with protic substrates (hydroamination, hydrophosphination, hydroacetylenation, and hydroalkoxylation) and hydridic substrates (hydrogenation, hydrosilylation, and hydroboration). The final section covers the Group 2‐catalyzed dehydrocoupling of amines and silanes, as well as amine‐boranes. For each reaction, the emphasis is on major achievements and mechanistic insights, highlighting the breadth of reactivity and complexity of these processes. To conclude this review, a brief mention of the first example of magnesium‐promoted single‐electron transfer catalysis opens up new horizons for the future potential of this up‐and‐coming class of catalysts.

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Dearomatized BIAN Alkaline-Earth Alkyl Catalysts for the Intramolecular Hydroamination of Hindered Aminoalkenes

Cited by 41 publications

References 78 publications

Recent Developments in Homogeneous Organomagnesium Catalysis

Recent Developments in Homogeneous Organomagnesium Catalysis

Hydroamination of Alkenes

Magnesium and Calcium Complexes in Homogeneous Catalysis

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