Asymmetric synthesis of primary amines from alkenes and chiral chloronitroso sugar derivatives.

Braun, Heinz; Felber, H.; Kresse, G.; Ritter, A.; Schmidtchen, Franz P.; Schneider, A.

doi:10.1016/s0040-4020(01)86396-1

Cited by 30 publications

(16 citation statements)

References 17 publications

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“…Reactions of alkenes such as 120 with α-chloronitrosoalkanes of type 119 proceed under very mild conditions and result in the formation of nitrones 121 that can be easily hydrolyzed into hydroxylamines 122 (equation 86) 267 . Chiral carbohydrate-derived α-chloronitrosoalkenes 123 possess enhanced reactivity and produce good stereoselectivity in reaction with prochiral alkenes such as 124 (equation 87) 268 …”

Section: Brmentioning

confidence: 99%

Synthesis of Hydroxylamines

Melman

2010

Patai's Chemistry of Functional Groups

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Introduction Hydroxylamines through Hydrolysis of Hydroxamic Acids, Oximes and Nitrones Synthesis of Hydroxylamines through Alkylation and Arylation of other Hydroxylamines Hydroxylamines through Reduction Reactions Hydroxylamines through Addition to the C  N Double Bond of Oximes, Oxime Ethers and Nitrones Hydroxylamines through Addition to the N  O Double Bond of Nitroso and Nitro Compounds Hydroxylamines through Oxidation of Amines Hydroxylamines through Cycloaddition Reactions

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Section: Brmentioning

confidence: 99%

Synthesis of Hydroxylamines

Melman

2010

Patai's Chemistry of Functional Groups

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“…To minimize such problems, a frequently employed strategy involves the introduction of electron-withdrawing groups at the nitroso functionality to not only increase the enophilic reactivity, but also afford relatively stable hydroxylamine products that are useful for further transformation. In this regard, electron-poor enophiles, such as pentafluoronitrosobenzene,6 α-chloronitroso agents,7 acylnitroso agents8 and p -nitronitosobenzene 9 are often used.…”

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confidence: 99%

“…However, only limited examples of asymmetric nitroso ene reactions have been reported, either by use of a chiral auxiliary for stereo control,10 or using a -choronitroso sugar derivatives as chiral nitrosyl reagents 7. Recently, iminonitroso agents have attracted a great deal of interest.…”

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confidence: 99%

Iminonitroso ene reactions: experimental studies on reactivity, regioselectivity, and enantioselectivity

Yang

Miller

2010

Tetrahedron Letters

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Ene reactions of iminonitroso agents with olefins were investigated in both solution and solid phase. Reactions afforded allyl hydroxylamine products in up to 99% yield and with high regioselectivity. A Cu(I)-mediated enantioselective nitroso ene reaction gave an ene product with up to 40% ee.The nitroso ene reaction with alkenes constitutes a mild, valuable method for generation of allylamines, versatile and fundamental building blocks in organic synthesis, in an atom economical fashion (Scheme 1). 1 However, this method has received relatively little attention compared to ene reactions with other enophiles such as singlet oxygen ( 1 O 2 ) 2 , azo compounds 3 and carbonyl functionalities, 4 presumably due to the labile nature of the resulting hydroxylamine products. 5 To minimize such problems, a frequently employed strategy involves the introduction of electron-withdrawing groups at the nitroso functionality to not only increase the enophilic reactivity, but also afford relatively stable hydroxylamine products that are useful for further transformation. In this regard, electron-poor enophiles, such as pentafluoronitrosobenzene, 6 α-chloronitroso agents, 7 acylnitroso agents 8 and pnitronitosobenzene 9 are often used.Enantioselective nitroso ene reactions would offer an attractive pathway to valuable, optically active amines from readily available olefins. However, only limited examples of asymmetric nitroso ene reactions have been reported, either by use of a chiral auxiliary for stereo control, 10 or using a-choronitroso sugar derivatives as chiral nitrosyl reagents. 7 Recently, iminonitroso agents have attracted a great deal of interest. Unlike the transient acylnitroso species, most iminonitroso agents, in particular, pyridinylnitroso derivatives, can be synthesized from commercially available amine precursors and stored in pure form. 11 Their successful application in Diels-Alder reactions, including enantioselective versions, 12 encouraged us to examine their reactivity in ene chemistry, which, surprisingly, has not been disclosed. Herein, we report studies of the reactivity and regioselectivity of iminonitroso agents with various olefins in ene reactions. We also describe preliminary results from solid phase supported nitroso ene reactions as well as enantioselective nitroso ene reactions.To begin our investigation, a panel of iminonitroso agents 1a-e were synthesized based on a literature reported procedure. 11 The unsymmetrical alkene, 2-methyl-2-butene 2a, was used as a model olefin substrate to examine the reactivity of enophiles 1a-e in the ene reaction. The Publisher's Disclaimer: This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final citable form. Please note that during the production process errors may be discovered which could affect the content, and ...

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“…[139] Scheme 34 Synthesis of N-(Aminoalkyl)hydroxylamines [139] 48−67% The disadvantage of hydroxylamines of type 111 is that they are susceptible to oxidation and disproportionation, but this is not observed for products derived from electron-deficient a-chloro-a-nitroso compounds. [143][144][145][146][147][148][149][150][151] For example, reaction of 2-chloro-2-nitrosoadamantane (112) with isopropenylbenzene gives, by hydrochloride elimination from transient 113, the nitrone hydrochloride 114, which upon hydrolysis provides the respective N-(2-phenylallyl)hydroxylamine hydrochloride (115) along with adamantan-2-one (116) (Scheme 36). [143] Scheme 36 Synthesis of N-(2-Phenylallyl)hydroxylamine [143] rt, 10 d 1-Chloro-1-nitrosocyclohexane is a convenient reagent for the asymmetric synthesis of a-(hydroxyamino) acids 120.…”

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confidence: 99%