Investigation of thermally induced .alpha.-deoxysilylation of organosilylated hydroxylamine derivatives as a general method for nitrene production

Chang, Young Hwan; Chiu, Fang-Ting; Zon, Gerald

doi:10.1021/jo00315a024

Cited by 31 publications

(9 citation statements)

References 4 publications

(6 reference statements)

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“…The traditional method for accessing acyl urea is the transformation of amides with phenyl carbamates, which produces stoichiometric phenol as a byproduct . Other approaches involve the coupling of isocyanates with amides and acyl isocyanates with amines, both of which usually require the use of unfriendly phosgene . Pd-catalyzed carbonylation has also been well-established as one of the most important ways to introduce a CO group into organic molecules .…”

Section: Introductionmentioning

confidence: 99%

Pd-Catalyzed Carbonylation of Acyl Azides

Huang

et al. 2019

J. Org. Chem.

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Pd-catalyzed reactions of azides with CO to access an isocynate intermediate have been developed extensively in recent years. However, the catalytic carbonylation of sensitive acyl azides has not been reported. Herein, we report a simple Pdcatalyzed carbonylation reaction of acyl azides with broad substrate scope, high efficiency, and simple operation under mild conditions, which provides facile access to acyl ureas. In addition, a mechanistic study was carried out by both experiment and DFT calculation. Control experiments and kinetic study revealed that the real active palladium species were Pd(0). The result of kinetic study suggested that palladium catalyst, azide, and CO were all involved in the turnover-limiting step except for amine. Further DFT study suggested that an unprecedented five-membered palladacycle intermediate was the key intermediate in the carbonylation reaction.

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Section: Introductionmentioning

confidence: 99%

Pd-Catalyzed Carbonylation of Acyl Azides

Huang

et al. 2019

J. Org. Chem.

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“…This includes the a-fluoromethylsilanes, which form fluorosilanes upon expulsion of carbene, [1] as well as the nitrene generators that are based on silylhydroxylamines such as R 3 SiN(R)OSiR 3 , [2] and which lead to the formation of stable siloxanes. a-Aminocarbosilanes are particularly sensitive to hydrolysis of the Si À C bond.…”

Section: Introductionmentioning

confidence: 99%

“…In the same conformation, but as the free molecule (gas phase), the Si¥¥¥N interaction is much weaker, and is characterized by an oxygen atom valence angle of 87.1 (9)8. This interaction is found to be even weaker in the gauche conformer (Si-O-N Abstract: The simple silylhydrazines F 3 SiN(Me)NMe 2 (1), F 2 Si(N-(Me)NMe 2 ) 2 (2), and F 3 SiN(SiMe 3 )NMe 2 (3) have been prepared by reaction of SiF 4 with LiN(Me)NMe 2 and LiN(SiMe 3 )NMe 2 , while F 3 SiN(SnMe 3 )NMe 2 (4) was prepared from SiF 4 and (Me 3 Sn) 2 NNMe 2 (5). The compounds were characterized by gasphase IR and multinuclear NMR spectroscopy ( 104.7(11)8).…”

Section: Introductionmentioning

confidence: 99%

Strong Intramolecular Secondary Si⋅⋅⋅N Bonds in Trifluorosilylhydrazines

Vojinović

McLachlan

Hinchley

et al. 2004

Chemistry A European J

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The simple silylhydrazines F(3)SiN(Me)NMe(2) (1), F(2)Si(N(Me)NMe(2))(2) (2), and F(3)SiN(SiMe(3))NMe(2) (3) have been prepared by reaction of SiF(4) with LiN(Me)NMe(2) and LiN(SiMe(3))NMe(2), while F(3)SiN(SnMe(3))NMe(2) (4) was prepared from SiF(4) and (Me(3)Sn)(2)NNMe(2) (5). The compounds were characterized by gas-phase IR and multinuclear NMR spectroscopy ((1)H, (13)C, (14/15)N, (19)F, (29)Si, (119)Sn), as well as by mass spectrometry. The crystal structures of compounds 1-5 were determined by X-ray crystallography. The structures of free molecules 1 and 3 were determined by gas-phase electron diffraction. The structures of 1, 2, and 4 were also determined by ab initio calculations at the MP2/6-311+G** level of theory. These structural studies constitute the first experimental proof for the presence of strong Si.N beta-donor-acceptor bonds between the SiF(3) and geminal NMe(2) groups in silylhydrazines. The strength of these non-classical Si.N interactions is strongly dependent on the nature of the substituent at the alpha-nitrogen atom of the SiNN unit, and has the order 3>4>1. The valence angles at these extremely deformed alpha-nitrogen atoms, and the Si.N distances are (crystal/gas): 1 104.2(1)/106.5(4) degrees, 2.438(1)/2.510(6) A; 3 83.6(1)/84.9(4) degrees, 2.102(1)/2.135(9) A; 4 89.6(1) degrees, 2.204(2) A.

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“…Alternatively, hydroxylamine 14 can also be synthesized via use of hexamethyldisilazane; however, the yield is only 18%. 23,24 A way to solve these problems is to apply the concept of 'counterattack reagents'.…”

Section: Counterattack Versus Traditional Methodsmentioning

confidence: 99%