Mechanism of the pseudo-molecular rearrangement of triethyl N-phenylphosphorimidate to diethyl N-ethyl-N-phenylphosphoramidate

Challis, Brian C.; Challis, J. A.; Iley, Jim

doi:10.1039/p29780000813

Cited by 23 publications

(21 citation statements)

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“…This product arises from the known rearrangement of sulfonimidates. [45] The reaction proved very sensitive to steric hindrance: while the rate diminished with 2-propanol ( Table 4, entry 3), no reaction took place in tertbutyl alcohol (Table 4, entry 8). This could be explained by the impossible solvolysis of iodosobenzene, which is an insoluble polymeric material: when alcohols are too sterically demanding, dialkoxyiodosobenzene could not be formed and the reaction could not proceed.…”

Section: Resultsmentioning

confidence: 98%

“…Products (R)-10 and (R)-12 were resubmitted to the reaction conditions: they neither isomerize nor react in the reaction vessel or on silica for periods of time much longer than the reaction time (but eventually slowly tautomerize into sulfonamides [45] ). Thus, maybe the mechanism is slightly different than the one inspired from the literature.…”

Section: Resultsmentioning

confidence: 99%

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Iodine(III)‐Mediated Preparations of Nitrogen‐Containing Sulfur Derivatives: Dramatic Influence of the Sulfur Oxidation State

Leca

Song

Amatore

et al. 2004

Chemistry A European J

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Reaction of sulfonamides with iodosobenzene leads to phenyliodinanes. A new catalysis reaction of the decomposition of these products in the presence of sulfoxides that allows the smooth synthesis of sulfoximines has been evidenced and studied: copper(II) salts were used to prepare compounds 4 a-j and 5 b, d, f, j, k from the corresponding, easily prepared, sulfoxides. The reactions proceed with retention of configuration at the sulfur center, and copper(II) triflate is the best candidate for the catalyst for the imination. Switching from sulfonamides to sulfinamides in the preparation of the starting iodinanes completely alters the reaction pathway: iodinanes are no longer accessible, and sulfonimidates 7 a-j are obtained instead. This behavior can be rationalized by the increase in pK(a) brought about by the removal of one oxygen atom from the sulfur center. Sulfonimidates are interesting molecules with varied applications. Optimization of their one-pot synthesis has been achieved by carrying out the reaction in acetonitrile. The stereochemical study has shown that the transformation proceeds with global retention of the configuration at the sulfur center, albeit with erosion of the enantiomeric purity. A model accounting for this outcome is proposed. In addition, the presence of oxidized sulfonamide by-products has been explained, and this latter pathway becomes the sole one when alcohol is replaced by water. Good yields of the oxidized products are obtained.

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Iodine(III)‐Mediated Preparations of Nitrogen‐Containing Sulfur Derivatives: Dramatic Influence of the Sulfur Oxidation State

Leca

Song

Amatore

et al. 2004

Chemistry A European J

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“…12 Starting from PhCON = P(OR) 3 , a dealkylation reaction was also observed by these authors. 12 Starting from PhCON = P(OR) 3 , a dealkylation reaction was also observed by these authors.…”

Section: Methodsmentioning

confidence: 70%

Synthesis ofN-Phosphorylsulfamates (as Pyrophosphate and Carbamylphosphate Analogues) through an Imidate-Amidate Rearrangement

2000

Synlett

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The sulfamates R-X-SO 2 -NH 2 (X = O, NH) derived from amino acids or n-octanol react easily with trialkylphosphites in the presence of diisopropylazodicarboxylate (DIAD) to give phospha-l 5 -azenes R-X-SO 2 -N = P(OR') 3 . Under basic conditions (DABCO), these derivatives are isomerized with loss of an alkyl group to N-phosphorylsulfamates R-X-SO 2 -NH-PO (OR') 2 . Such structure can be regarded as a bioisoster of pyrophosphate or carbamoylphosphate.

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“…N-Alkyl and aryl-bearing phosphoranimines will generally thermally rearrange by what is thought to be a multicenter intramolecular react i~n .~~ This rearrangement is catalyzed by electrophiles, and the mechanism is supported by kinetic data. 25 In contrast, evidence indicates that the thermal isomerization of permethoxylated cyclic phosphazene trimer and tetramer is intermolecular and self-catalyzed. 26 The isomerization of N-silyl-bearing phosphoranimines has been little studied.…”

Section: Introductionmentioning

confidence: 94%

Synthesis, isomerization, and polymerization of mixed phosphoranimines

White

Matyjaszewski

1996

J. Polym. Sci. A Polym. Chem.

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Mechanism of the pseudo-molecular rearrangement of triethyl N-phenylphosphorimidate to diethyl N-ethyl-N-phenylphosphoramidate

Abstract: I n accord with recent practice ' phosphyl' is used as a collective term to include phosphoryl, phosphonyl, and yhosphinyl groups.

Cited by 23 publications

References 0 publications

Iodine(III)‐Mediated Preparations of Nitrogen‐Containing Sulfur Derivatives: Dramatic Influence of the Sulfur Oxidation State

Iodine(III)‐Mediated Preparations of Nitrogen‐Containing Sulfur Derivatives: Dramatic Influence of the Sulfur Oxidation State

Synthesis ofN-Phosphorylsulfamates (as Pyrophosphate and Carbamylphosphate Analogues) through an Imidate-Amidate Rearrangement

Synthesis, isomerization, and polymerization of mixed phosphoranimines

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