ChemInform Abstract: Reactions of 2‐Chloroalkaneimines with Trialkylphosphites and Triphenylphosphine.

Sinitsa, A. D.; Krishtal, V. S.; Momot, V. V.; Maidanovich, N. K.; Kal'chenko, V. I.

doi:10.1002/chin.198643223

Cited by 1 publication

(5 citation statements)

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“…Imidoyl chloride 82 should be less active, as the imine nitrogen atom and trifluoroacetyl group are separated by an oxygen atom (for OCOCF 3 p 0.46 [36] 3 The presence of labile hydrogen atoms in fluoroacetimidoyl chloride 88 offers additional synthetic possibilities. It was shown that its reaction with triethyl phosphite is accompanied by 1,3-prototropic shift to form a mixture (~1:1) of imidoylphosphonates 90a and isomeric C-phosphorylated fluorovinyl amide 91a [38] (Scheme 29).…”

Section: -90%mentioning

confidence: 99%

“…The ratio of the N-and C-phosphorylation products (118/119) is virtually independent of the steric properties of the substituent at the carbonyl group (R = Me or t-Bu), and increases with the electron-withdrawing capacity of the alkoxy group (CF 3 …”

Section: N-acyltrichloroacetimidoyl Chloridesmentioning

confidence: 99%

“…Thus, chloroimine 1 reacts with triethylphosphite under harsh conditions affording, exclusively, isomeric products of Cphosphorylation at haloalkyl (2) or imine (3) carbon atoms respectively [3] (Scheme 1).…”

Section: Nucleophilic Phosphorylation Of N-alkyl- N-h and N-trimethmentioning

confidence: 99%

“…Reactivity increases with the growth in electronwithdrawing properties of the haloalkyl group, and the reaction route is altered: N-H (4) and N-trimethylsilyl imines 5,6 react exothermally with trialkylphosphites or triphenylphosphine to give iminophosphorane (7,8), products of Nphosphorylation (Scheme 2) [3,4].…”

Section: Nucleophilic Phosphorylation Of N-alkyl- N-h and N-trimethmentioning

confidence: 99%

“…The nature of the phosphorus reagent controls both the rate of formation of 137 and the subsequent conversions (Scheme 46)[49].While compounds 138 and 139 are generated from dealkylation at the pentacoordinate P atom of 137, dealkylation is impossible in the case of phosphoranes with R = Ph, PhO, and their decomposition occurs by elimination of R3 PO and subsequent transformations of intermediate nitrile-ylide 140.It is significant that the behavior of compound 136 in the reactions with P III nucleophiles substantially differs from that of both N-benzoyltrifluoroacetimidoylphosphonate 64 (X = P(O)(OEt) 2 , (Scheme 18) and N-formyltrichloroacetimidoylphosphonate 132 (Scheme 45), all containing substituents at the C-and N-atoms of the C=N bond, close in electronic parameters.…”

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confidence: 99%

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Phosphorylation of α-Haloimines: P-C vs. P-N Bond Formation

Onys’ko¹,

Rassukana²,

Sinitsa

2008

COC

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The chemoselectivity of reactions between -haloimines -compounds containing a Hal-C-C=N-skeleton -and nucleophilic phosphorus derivatives are discussed systematically. The synthetic potentialities, as well as possible mechanistic pathways of this currently developing field of organophosphorus chemistry are considered. Phosphorylation of the -haloimines leads mainly to C-or N-phosphorylated compounds as the final products, the selectivity being dependent on the type of halogen, substituents at the imine carbon and nitrogen atoms, and on the nature of phosphorus reagent. The main factors controlling regio-and stereoselectivity are elucidated. A series of novel theoretically and preparatively important transformations have also been illustrated; i.e., new diad rearrangements involving the N C and C N transfer of a sulfonyl or a phosphoryl group, the unusual acylation of the electrophilic imine carbon atom by tervalent phosphorus isocyanates, and others. Variety of transformations is connected with the possible participation of C=N bond, halogen atoms or N-substituents, in reactions involving the Hal-C-C=N-arrangement. The use of haloimines as versatile building blocks for synthesis of practically promising functionalized aminophosphonates, bisphosphonates, and phosphorus analogs of dehydro aminoacids, etc., is demonstrated.

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Section: -90%mentioning

confidence: 99%

Section: N-acyltrichloroacetimidoyl Chloridesmentioning

confidence: 99%