Regioselective differentiation of vicinal methylene C–H bonds enabled by silver-catalysed nitrene transfer

Scamp, Ryan J.; Scheffer, Bradley; Schomaker, Jennifer M.

doi:10.1039/c9cc04006d

Cited by 20 publications

(9 citation statements)

References 49 publications

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“…[33] Retention of the crystallographically observed dimeric structure was supported by DOSY-NMR spectroscopy,a nd the authors proposed that the sterically hindered dinuclear "pocket" of the catalyst accounts for its selectivity in catalysis.T he initial report of this catalyst demonstrated selectivity for amination of propargylic,b enzylic,a nd allylic CÀHb onds over tertiary alkyl CÀHb onds (Figure 12 b). [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.…”

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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Section: Methodsmentioning

confidence: 99%

Dinuclear Silver Complexes in Catalysis

2021

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“…reported silver‐catalyzed benzosultam formation by selective differentiation of vicinal methylene C−H bonds (Scheme 100). The process has salient features which include‐(1) use of sulphonamide precursors to avoid potentially explosive azides, (2) the ability to enhance regioselectivity through electronics, (3) proclivity for amidation of homobenzylic C−H bonds over their weaker benzylic neighbours, (4) the ability to tune regioselectivity in bulk substrates via orthogonal electronic and steric control [105] …”

Section: Transformations Involving Hypervalent Iodine Reagents and 2 ...mentioning

confidence: 99%

Combined Approach of Hypervalent Iodine Reagents and Transition Metals in Organic Reactions

et al. 2022

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This review outlines the progress over recent years in the reactions involving combined approach of hypervalent iodine reagents and transition metals such as palladium, nickel, iridium, gold, rhodium, copper, iron, ruthenium, platinum, silver, zinc, rhenium and cobalt. This approach enables organic transformations complimentary to traditional manifolds. Hypervalent iodine reagents play a preeminent role in organic chemistry due to their versatile reactivity, heteroatom ligands and mild reaction conditions. These reagents in combination of transition metal compounds are used in many synthetically useful organic reactions such as oxidation, rearrangement, amination, halogenation, amidation, ring-opening, cyclization and CÀ H and CÀ C functionalization reactions, etc. which are discussed here. Combination with Cobalt 2.3. Reactions of Hypervalent Iodine Reagents with Copper 2.4. Reactions of Hypervalent Iodine Reagents in Combination with Nickel 2.5. Reactions of Hypervalent Iodine Reagents in Combination with Zinc 3. Transformations Involving Hypervalent Iodine Reagents and 2 nd Transition Series Metals 3.1. Reactions of Hypervalent Iodine Reagents in Combination with Ruthenium 3.2. Reactions of Hypervalent Iodine Reagents in Combination With Rhodium 3.3. Reactions of Hypervalent Iodine Reagent in Combination With Palladium 3.4. Reactions of Hypervalent Iodine Reagents in Combination with Silver 4. Transformations Involving Hypervalent Iodine Reagents and 3rd Transition Series Metals 4.1. Reactions of Hypervalent Iodine Reagents in Combination with Rhenium 4.2. Reactions of Hypervalent Iodine Reagents in Combination with Iridium 4.3. Reactions of Hypervalent Iodine Reagents in Combination with Platinum 4.4. Reactions of Hypervalent Iodine Reagents in Combination with Gold 5. Conclusion

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“…Substrate 79 , which contains both benzylic and homobenzylic C–H bonds, was employed for silver-catalyzed amination using either Py 5 Me 2 or t Bu 3 tpy as the ligand (Table ). Utilizing [(Py 5 Me 2 )AgOTf] 2 resulted in preferred insertion at the benzylic position to form the five-membered sultam, while [( t Bu 3 tpy)AgOTf] 2 favored the formation of the six-membered sultam. Interestingly, an increasing amount of benzylic amination was observed with Py 5 Me 2 when the steric bulk at the ζ-carbon was increased, suggesting that the steric bulk of the catalyst is likely the key factor in the selectivity.…”

Section: Regioselective Nitrene Transfermentioning

confidence: 99%

Tunable Silver-Catalyzed Nitrene Transfer: From Chemoselectivity to Enantioselective C–H Amination

et al. 2022

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Transition-metal-catalyzed C–H aminations via nitrene transfer processes are powerful synthetic methods to construct valuable amines. Over the past decade, significant efforts in the field have resulted in an expansion in the utility of nitrene transfer chemistry, enabling the use of these carbon–nitrogen bond-forming reactions in complex organic molecule syntheses. This Perspective highlights efforts in silver-catalyzed nitrene transfer reactions that achieve chemo-, site-, and enantioselective transformations using simple N-dentate ligands that can serve as stepping stones for future investigations of other tunable C–H functionalizations.

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Regioselective differentiation of vicinal methylene C–H bonds enabled by silver-catalysed nitrene transfer

Abstract: Silver-catalyzed nitrene insertion enables the formation of benzosultams in good yield and with regioselectivity complementary to other transition metal nitrene-transfer catalysts.

Cited by 20 publications

References 49 publications

Dinuclear Silver Complexes in Catalysis

Dinuclear Silver Complexes in Catalysis

Combined Approach of Hypervalent Iodine Reagents and Transition Metals in Organic Reactions

Tunable Silver-Catalyzed Nitrene Transfer: From Chemoselectivity to Enantioselective C–H Amination

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