Tunable catalyst-controlled syntheses of β- and γ-amino alcohols enabled by silver-catalysed nitrene transfer

Ju, Minsoo; Huang, Minxue; Vine, Logan E.; Dehghany, Mahzad; Roberts, Jessica M.; Schomaker, Jennifer M.

doi:10.1038/s41929-019-0339-y

Cited by 44 publications

(34 citation statements)

References 47 publications

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“… 5 − 9 As a result, there are numerous approaches to their synthesis. 10 − 13 A powerful approach for the arylation of olefins is the Mizoroki–Heck (MH) reaction, 14 , 15 though internal olefin substrates often require directing groups to achieve reasonable regioselectivity. 16 − 19 In the case of allylamine substrates, protection of the amine has been required ( Scheme 1 a) to achieve these reactions, 20 − 24 and the reactions are limited to a single arylation except in a few circumstances ( Scheme 1 b).…”

mentioning

confidence: 99%

Palladium-Catalyzed Regioselective Arylation of Unprotected Allylamines

Landge

Maxwell

Chand-Thakuri

et al. 2020

JACS Au

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Palladium-catalyzed organometallic transformations of free amines are often unsuccessful due to side reactions, such as oxidation, that can occur. However, the ability to furnish the free amine products from these reactions is important for improving the utility and sustainability of these processes, especially for accessing their potential as medicinal and agrochemical agents. Notably, the 3,3-diarylallylamine motif is prevalent in a variety of biologically relevant structures, yet there are few catalytic approaches to their synthesis, and none involving the free amine. Herein, we describe a simple protocol for the arylation of cinnamylamines and the diarylation of terminal allylamines to generate a diverse group of 3,3-diarylallylamine products using a Pd II precatalyst. Key features of the method are the ability to access relatively mild conditions that facilitate a broad substrate scope as well as direct diarylation of terminal allylamine substrates. In addition, several complex and therapeutically relevant molecules are included to demonstrate the utility of the transformation.

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confidence: 99%

Palladium-Catalyzed Regioselective Arylation of Unprotected Allylamines

Landge

Maxwell

Chand-Thakuri

et al. 2020

JACS Au

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“…Initial investigations into high coordinate ligands for Ag-catalyzed NT, including tpa, gave a strong preference for amidation at the  site (Scheme 10). 33 Interestingly, changing the ligand/metal ratio of Me 4 phen from 2:1 to 1:1 reversed the site selectivity from  to , just as it reversed chemoselectivity in previous studies with similar ligands. This led us to explore other bidentate N-donors in 1:1 ligand/metal ratios, including neocuproine and a dimethyl-substituted bis(oxazoline) ligand, dmbox.…”

Section: Choosing Between Similar C-h Bondsmentioning

confidence: 58%

“…We have demonstrated that our methodologies are compatible with complex molecules of biological relevance and thus have high values for derivatization and analogue synthesis (Scheme 12). 33 Among tested molecules are nonsteroidal anti-inflammatory drugs oxaprozin and nabumetone as well as essential omega-6 fatty acid linoleic acid that can be subsequently ring opened into the corresponding amino alcohols.…”

Section: Late-stage Functionalizations Using Silver-catalyzed Nitrenementioning

confidence: 99%

Taming Nitrene Reactivity with Silver Catalysts

Vine¹,

Zerull²,

Schomaker³

2020

Synlett

Self Cite

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Nitrene transfer (NT) is a convenient strategy to directly transform C–H bonds into more valuable C–N bonds and exciting advances have been made to improve selectivity. Our work in silver-based NT has shown the unique ability of this metal to enable tunable chemo-, site-, and stereoselective reactions using simple N-dentate ligand scaffolds. Manipulation of the coordination environment and noncovalent interactions around the silver center furnish unprecedented catalyst control in selective NT and provide insights for further improvements in the field.1 Introduction1.1 Strategies for Nitrene Transfer1.2 Brief Summary of Chemocatalyzed Nitrene Transfer1.3 Focus of this Account2 Challenges in Chemocatalyzed Nitrene Transfer2.1 Reactivity Challenges2.2 Selectivity Challenges2.3 Chemoselective Nitrene Transfer2.4 Site-Selective Nitrene Transfer2.5 Enantioselective Nitrene Transfer3 Summary and Perspective3.1 Future Opportunities and Challenges3.2 Conclusion

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“…[33] TheS chomaker group subsequently reported the use of this catalyst in astudy regarding differentiation of benzylic versus homobenzylic C À Hbond amidation (Figure 12 c), [34] as well as in the catalyst-controlled synthesis of b-o rg-amino alcohols via CÀHb ond amidation (Figure 12 d). [35] In the latter example,t he bulky Py 5 Me 2 ligand provided opposite selectivity as compared to aless sterically hindered bis(oxazoline) ligand. At ransition state model for selective b-C-H amidation was proposed based on the crystal structure of the catalyst.…”

Section: Methodsmentioning

confidence: 99%

Dinuclear Silver Complexes in Catalysis

2021

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Over the past two decades, there has been a substantial increase in the number of synthetically useful transformations catalyzed by silver. Across the range of silver‐catalyzed reactions that have been reported, dinuclear species often emerge as a common feature, either as the (pre‐)catalysts themselves or as intermediates during catalysis. This Minireview explores the role of dinuclear silver complexes in homogeneous catalysis, which we hope will aid in the development of improved design principles for silver catalysts.

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Tunable catalyst-controlled syntheses of β- and γ-amino alcohols enabled by silver-catalysed nitrene transfer

Cited by 44 publications

References 47 publications

Palladium-Catalyzed Regioselective Arylation of Unprotected Allylamines

Palladium-Catalyzed Regioselective Arylation of Unprotected Allylamines

Taming Nitrene Reactivity with Silver Catalysts

Dinuclear Silver Complexes in Catalysis

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