The reaction of n-chloroethanesulfonamide with 1-hexene

Ohashi, Takeki; Sugie, Masahiro; Okahara, Mitsuo; Komori, Saburô

doi:10.1016/s0040-4039(00)75406-2

Cited by 12 publications

(4 citation statements)

References 3 publications

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“…They have already been described (12b). Hydrogenation of 1 ,2-adduct 41b over Adam's catalyst in ethyl acetate afforded the corresponding norbornane derivative 456 (Scheme 13) which was different from either of the 1,2-adducts 106 and 116 obtained from the photochemical addition of NCA (16) to norbornene (see Scheme 8). Therefore, the chloroacetamido group of 45b must be endo.…”

Section: Additions To Dienesmentioning

confidence: 99%

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The photochemical addition of N-haloamides to olefins: the influence of various factors on the competition between 1,2-addition and hydrogen abstraction

Lessard¹,

Mondon²,

Touchard³

1981

Can. J. Chem.

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Thispaper is dedicated to Prof. Raymond U. Lemieux on the occasion of his 60th birthday JEAN LESSARD, MARTINE MONDON, and DANIEL TOUCHARD. Can. J. Chem. 59,431 (1981). In the photodecomposition of N-haloamides (ZCONRX) in the presence of olefins, the 1,2-addition chain competes with the hydrogen abstraction chain(s) leading to the parent amide (the quantum yields for these processes are greater than unity). The following factors were shown to have an influence on this competition as measured by the yield of 1 ,2-addition and the yield of parent amide in methylene chloride solutions: (i) the N-halogen (higher yields of addition with X = C1 than with X = Br); (ii) the electronegativity of Z (increase of the yield of addition as the electronegativity of Z increases); (iii) the temperature (higher yields of addition at lower temperatures, and at -70°C, better yields of addition (>90%, R = H) for X = Br than for X = CI); and (iu) the size of R (dramatic decrease of the yield of 1,2-addition in going from R = H to R = CH,). Surprisingly, the presence of a scavenger for HX had no influence on the yield of 1,2-addition. Both the size and electronegativity of Z had an effect on the stereochemistry of 1,2-addition to cyclohexene. High yields of addition to a variety of olefins were obtained with N-chloroamides such as CICH,CONHCI, C,H,OCONHCI, CF,CONHCI. Their addition to en01 ethers at -70°C led to the synthesis of a-amido acetals o r ketals (aldehydes or ketones) and to an a-amido glycoside in good yields.

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Section: Additions To Dienesmentioning

confidence: 99%

“…Closely related are the photochemical addition to olefins of N-halo-succinimides (13,14) and -glutarimides (13), of N,N-dichlorosulfonamides (IS), of N-alkyl-N-chlorosulfonamides (16,17), of N-chloro-N-methylcyanamide (17), and the spontaneous addition of N,N-dihalophosphoramides (18).…”

Section: Imentioning

confidence: 99%

The photochemical addition of N-haloamides to olefins: the influence of various factors on the competition between 1,2-addition and hydrogen abstraction

Lessard¹,

Mondon²,

Touchard³

1981

Can. J. Chem.

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“…styrenes), metal catalyzed (Cr, Cu) amination reactions, and in rare cases photoactivated using UV irradiation under cryogenic and oxygen-free conditions. [12][13][14][15][16] Herein we demonstrate that Cl2NBoc (1) is much more useful reagent than previously thought, as it can be directly photoactivated with blue light -circumventing numerous prior issues related to generation of N-centered neutral radicals -to aminochlorinate unactivated olefins (2) to 1,2-chloro-N-Cl compounds 3 (Scheme 1A).…”

mentioning

confidence: 82%

Blue Light-Induced 1,2-Aminochlorination of Olefins using Dichlorocarbamates

Irvankoski,

Davenport,

Ess

et al. 2023

Preprint

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Activation of N,N-dichlorocarbamates with blue light facilitates a direct 1,2-aminochlorination of unactivated olefins to yield 1,2-chloro-N-Cl-carbamates under ambient conditions. Mechanistic studies suggest that N,N-dichlorocarbmates undergo a photochemical excitation to yield a neutral nitrogen-centered radical, which rapidly reacts with olefins in an anti-Markovnikov fashion. Using the method, a range of functionally diverse substrates are successfully aminochlorinated to yield the corresponding 1,2-chloro-N-Cl compounds.

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“…Addition reactions with N -alkyl- N -halosulfonamides to unsaturated compounds have not been examined in detail so far. In earlier works Komori added a secondary N -chloro-sulfonamide to 1-hexene under photoirridation [ 12 – 13 ] and Priestly [ 14 ], Seden [ 15 ] and Daniher [ 16 ] published addition reactions of secondary N -halosulfonamides and N , N -dihalosulfonamides to alkenes. Neale [ 17 ] discussed a radical mechanism via nitrogen radicals as intermediates.…”

Section: Introductionmentioning

confidence: 99%

Intermolecular addition reactions of N-alkyl-N-chlorosulfonamides to unsaturated compounds

Heuger¹,

Göttlich²

2015

Beilstein J. Org. Chem.

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Summary N-Alkyl-N-chlorosulfonamides add to alkenes under copper(I) catalysis. In reactions of styrene derivatives with terminal double bonds the addition products were obtained in excellent yield and high regioselectivity. Lower yields are obtained in addition reactions to non-aromatic alkenes. The reaction most likely proceeds via a redox catalysis and amidyl radicals, a concerted mechanism has been ruled out and a polar mechanism via chloronium ions would lead to the opposite regiochemistry.

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The reaction of n-chloroethanesulfonamide with 1-hexene

Cited by 12 publications

References 3 publications

The photochemical addition of N-haloamides to olefins: the influence of various factors on the competition between 1,2-addition and hydrogen abstraction

The photochemical addition of N-haloamides to olefins: the influence of various factors on the competition between 1,2-addition and hydrogen abstraction

Blue Light-Induced 1,2-Aminochlorination of Olefins using Dichlorocarbamates

Intermolecular addition reactions of N-alkyl-N-chlorosulfonamides to unsaturated compounds

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