The stereochemistry of the aryl phosphate/aryl phosphonate rearrangement in 1,3,2-oxazaphospholidine 2-oxides

Welch, Steven C.; Levine, Jeffrey A.; Bernal, Ivan; Cetrullo, James

doi:10.1021/jo00311a017

Cited by 21 publications

(8 citation statements)

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“…These results show similar stereospecificity of the rearrangement for the diazaphospholidine-borane complexes, with respect to the phosphate series [25] or the phosphiniteborane complexes. [20,26] As previously described, [12c,20,26] a mechanism involving a trigonal-bipyramidal (TBP) intermediate can be postulated (Scheme 7).…”

Section: Resultssupporting

confidence: 67%

Diastereoselective Synthesis of New P‐Stereogenic (ortho‐Hydroxyaryl)diazaphospholidine–Borane Complexes by a Totally Stereoselective P–O to P–C Migration Rearrangement

2006

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The totally diastereoselective synthesis of new P-stereogenic (o-hydroxyaryl)diazaphospholidines, in the form of their borane complexes 4a-4h, is described. The efficiency of this procedure is based both, on a one-pot and totally diastereoselective synthesis of the precursors (ortho-bromoaryloxy)diazaphosphospholidine-borane complexes 3a-3h, and on a stereoselective P-O to P-C migration rearrangement. A X-ray

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Section: Resultssupporting

confidence: 67%

Diastereoselective Synthesis of New P‐Stereogenic (ortho‐Hydroxyaryl)diazaphospholidine–Borane Complexes by a Totally Stereoselective P–O to P–C Migration Rearrangement

2006

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“…It is known, for example, for formyl-substituted ferrocenes that a second substitution of a monofunctionalized ferrocene with the same functionality leads to a summation of the electronic effects and, therefore, to a linear increase or decrease of the redox potential. 68 Molecule 34 containing two [3]ferrocenophane motifs, compared to two ferrocenyls at the phosphorus atom (33), showed two redox processes: a one-electron event for the non-bridged and a redox process with a shoulder including two one-electron processes for both [3]ferrocenophanes (Figure 7).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Reactivity of Ferrocenyl Phosphates Bearing (Hetero-)Aromatics and [3]Ferrocenophanes toward Anionic Phospho-Fries Rearrangements

2017

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The temperature-dependent behavior within anionic phospho-Fries rearrangements (apFr) of P(O)(OFc)(EAr) (Fc = Fe(η-CH)(η-CH); E = O; Ar = phenyl, naphthyls, (R)-BINOL, [3]ferrocenophanyl; E = N, 1H-pyrrolyl, 1H-indolyl, 9H-carbazolyl; n = 1-3) is reported. While Fc undergoes one, the Ph-based apFr depends on temperature. First, the aryls are lithiated and rearranged, followed by Fc and N-heterocycles. Addition of MeSO thus gave methylated Fc, contrary to non-organometallic aromatics giving mixtures of HO and MeO derivatives. The (R)-BINOL Fc phosphate gave Fc-rearranged phosphonate in 91% de. Exchanging O- with N-aliphatics prevented apFr, due to higher electron density at P. Also 1,2-N→C migrations were observed. X-ray analysis confirms 1D H bridge bonds for OH and NH derivatives. The differences in reactivity between N-aliphatic and N-aromatic phosphoramidates were verified by electrochemistry. The redox potentials revealed lower values for the electron-rich aliphatics, showing no apFr, preventing a nucleophilic attack at P after lithiation. Redox separations for multiple Fc molecules are based on electrostatic interactions.

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“…Such behaviour is typical of oxazaphospholidines. 27,28 Both epimers adopt an envelop conformation. The flap atom, the CHPh carbon, is out of the plane formed by O1-P1-N2-C12, in Fig.…”

Section: Resultsmentioning

confidence: 99%

Another side of the oxazaphospholidine oxide chiral ortho-directing group

et al. 2012

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A new ferrocenyl oxazaphospholidine oxide 3 was synthesized together with its P-epimer 2 in the reaction of ferrocene lithium with phosphoramidite chloride 1. 3 was successfully derivatized into planar chiral 1,2-ferrocenes, including phosphine ligands, via highly diastereoselective ortho-lithiation and subsequent functionalization; these compounds display opposite planar chirality to those obtained from 2. Some of these 1,2-ferrocenes were further lithiated, allowing for the introduction of a free phosphine group at the oxazaphospholidine ring. The X-ray structures of the compounds 2 and 3 as well as those of the new 1,2-ferrocenes 4 and 7 have been determined.

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The stereochemistry of the aryl phosphate/aryl phosphonate rearrangement in 1,3,2-oxazaphospholidine 2-oxides

Cited by 21 publications

References 0 publications

Diastereoselective Synthesis of New P‐Stereogenic (ortho‐Hydroxyaryl)diazaphospholidine–Borane Complexes by a Totally Stereoselective P–O to P–C Migration Rearrangement

Diastereoselective Synthesis of New P‐Stereogenic (ortho‐Hydroxyaryl)diazaphospholidine–Borane Complexes by a Totally Stereoselective P–O to P–C Migration Rearrangement

Reactivity of Ferrocenyl Phosphates Bearing (Hetero-)Aromatics and [3]Ferrocenophanes toward Anionic Phospho-Fries Rearrangements

Another side of the oxazaphospholidine oxide chiral ortho-directing group

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