The Totally Protected Hydroxy Containing α-Amino Phosphonic Esters and α-Amino Phosphinoxides as well as Their Carbamoyl Derivatives

Hatam, M.; Goerlich, Jens R.; Schmutzler, Reinhard; Gröger, Harald; Martens, Jürgen

doi:10.1080/00397919608003785

Cited by 9 publications

(6 citation statements)

References 38 publications

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“…The known approaches to the preparation of P(O) Me 2 -containing amines relied on the phospha-Mannich (the Kabachnik-Fields-type) reaction of the parent dimethyl phosphine oxide (HP(O)Me 2 ) with trimeric imines, which was used for the synthesis of two simplest acyclic (Nalkylaminomethyl)dimethylphosphine oxides (i. e. N-methyl-and N-benzyl). [30,31] Other literature methods involved reactions of HP(O)Me 2 with tetrasubstituted 2,5-dihydrooxazoles or 5,6dihydro-2H-1,3-oxazines, [32] aromatic imines, [33,34] or dipeptidederived aldehydes, [35] reactions of alkyl methylphosphonochloridates with the Grignard reagents, [36] as well as radical addition to the double bonds of enamides, [37] allyl amines/amides, [37,38] etc. [39] Firstly, we took an advantage of the phospha-Mannich reaction that was tested with cyclic imines 1 a-e (typically existing as their trimers).…”

Section: Resultsmentioning

confidence: 99%

“…Finally, ethylene homologue of 2 c, compound 30, was obtained via the base-mediated Michael addition of dimethylphosphine oxide to 2-vinylpyridine (31), followed by catalytic hydrogenation of dimethyl(2-(pyridin-2-yl)ethyl)phosphine oxide (32) with H 2 (50 atm) in the presence of HOAc and treatment with HCl-1,4-dioxane, which gave piperidine 30 • HCl as a hydrochloride in 58 % yield (Scheme 10).…”

Section: Resultsmentioning

confidence: 99%

“…Colorless solid, mp 165-167 °C. (32). Na (10.9 g, 0.476 mol) was carefully added in EtOH (200 mL), and the resulting solution was added dropwise to a mixture of 2-vinylpyridine (31, 50.0 g, 0.476 mol) and HP(O)Me 2 (37.1 g, 0.476 mol) in EtOH (400 mL).…”

Section: -(Dimethylphosphoryl)morpholin-4-ium Chloride (23)mentioning

confidence: 99%

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Heteroaliphatic Dimethylphosphine Oxide Building Blocks: Synthesis and Physico‐Chemical Properties

et al. 2021

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Scalable synthesis of saturated heterocyclic dimethyl phosphine oxides (derivatives of azetidine, pyrrolidine, piperidine, and morpholine) is disclosed. The key steps of the synthesis relied on the reactions of HP(O)Me 2 , i. e. the phospha-Mannich (the Kabachnik-Fields-type) condensation with cyclic imines or monoprotected diamines, palladium-catalyzed reactions of alkenyl halides or trifltates (generated from cyclic ketones), as well as base-mediated nucleophilic substitution, Michael addition, or oxirane ring opening. It was shown that introducing the P(O)Me 2 group into the saturated heterocyclic core had very strong impact on the compound's basicity: the corresponding α-, β-, and γ-isomeric derivatives were by ca. 4, 2, and 1.6 pK a units less basic, respectively, as compared to the parent saturated heterocycle. Meanwhile, the P(O)Me 2 -substituted compound was more basic than its SO 2 i-Pr and SO 2 NMe 2containing isosteres (by ca. 1.2 and 0.4 pK a units, respectively). It was also demonstrated that the P(O)Me 2 group typically increased the compound's hydrophilicity and aqueous solubility. In particular, the LogP values for the corresponding derivatives were by ca. 1.4-1.7 and 0.6 units lower than for the non-substituted counterpart and sulfonamide/sulfone isosteres, respectively. Finally, a potential of the synthesized building blocks to generate lead-like three-dimensional compound libraries was confirmed using the Nelson's LLAMA tool.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Heteroaliphatic Dimethylphosphine Oxide Building Blocks: Synthesis and Physico‐Chemical Properties

et al. 2021

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“…The oxazolidine-substituted alkenes 1a , b , e , f were synthesized by the condensation of the corresponding aldehyde with S -phenylglycinol in analogy to the reported procedure,12g followed by reaction with the appropriate aryl isocyanate (Scheme ) . The cis -disubstituted olefin 1d was obtained by partial catalytic hydrogenation of the alkyne 1g , which was synthesized from 2-pentynal, S -phenylglycinol, and phenylisocyanate (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

Efficient Control of the Diastereoselectivity and Regioselectivity in the Singlet-Oxygen Ene Reaction of Chiral Oxazolidine-Substituted Alkenes by a Remote Urea NH Functionality: Comparison with Dimethyldioxirane andm-Chloroperbenzoic Acid Epoxidations

Adam

Peters

et al. 2001

J. Am. Chem. Soc.

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The singlet-oxygen ene reaction and the epoxidation by DMD of chiral oxazolidine-substituted alkenes, equipped with a free urea NH functionality and a conformationally fixed double bond, proceed in high like diastereoselectivity (up to >95:5); also a high regioselectivity was found for the (1)O(2) ene reaction. Capping of the free NH functionality by methylation erases this like selectivity for both oxidants and significantly reduces the regioselectivity in the ene reaction. These data demonstrate effective hydrogen bonding between the remote urea NH functionality and the oxidant that favors the like attack on the C-C double bond. For (1)O(2), the hydrogen bonding in the exciplex results in preferred hydrogen abstraction from the alkyl group cis to the directing urea functionality.

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“…215 The addition of hydrophosphoryl compounds to 2H-1,4-benzothiazines and 2H-1,3-oxazolidines occurs under the same conditions. 100 Hydrophosphorylation of cyclic imines catalysed by chiral lanthanide catalysts results in a high de (up to 98%). 216 In the presence of chiral titanium catalyst, the reaction is nonstereospecific.…”

Section: A Addition Of Hydrophosphoryl Compounds To Iminesmentioning

confidence: 99%

The Kabachnik–Fields reaction: synthetic potential and the problem of the mechanism

1998

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The published data of the last decade concerning the mechanism of the Kabachnik ± Fields reaction and its significance for the chemistry of organophosphorus compounds as a method for the synthesis of a-amino phosphonates and their numerous functionally substituted derivatives and analogues, such as phosphinates and phosphine oxides, are generalised and systematised. The review discusses the classical version of the Kabachnik ± Fields reaction, its modifications with the use of phosphorus chlorides, neutral esters and inorganic phosphorus acids, as well as chemical processes simulating separate steps of the reaction, viz., hydrophosphorylation of imines and amination of a-hydroxy phosphonates. Data on the practical application of a-amino phosphonates are presented. The bibliography includes 253 references.

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The Totally Protected Hydroxy Containing α-Amino Phosphonic Esters and α-Amino Phosphinoxides as well as Their Carbamoyl Derivatives

Cited by 9 publications

References 38 publications

Heteroaliphatic Dimethylphosphine Oxide Building Blocks: Synthesis and Physico‐Chemical Properties

Heteroaliphatic Dimethylphosphine Oxide Building Blocks: Synthesis and Physico‐Chemical Properties

Efficient Control of the Diastereoselectivity and Regioselectivity in the Singlet-Oxygen Ene Reaction of Chiral Oxazolidine-Substituted Alkenes by a Remote Urea NH Functionality: Comparison with Dimethyldioxirane andm-Chloroperbenzoic Acid Epoxidations

The Kabachnik–Fields reaction: synthetic potential and the problem of the mechanism

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