Stereochemistry of nucleophilic attack on a cyclic phosphinate ester

Cremer, Sheldon E.; Trivedi, B. C.

doi:10.1021/ja01053a058

Cited by 20 publications

(12 citation statements)

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“…2 The trans isomer was obtained selectively. 4,20 Its stereochemistry was established by X-ray crystallography. 5 The generally accepted mechanism (Scheme 1) involves addition of a phosphenium ion at the 2-position of the olefin.…”

Section: The Mcbride Synthesis and Related Methodsmentioning

confidence: 99%

“…These reactions usually proceed with excellent stereoselectivity, with mainly retention of phosphorus configuration. 4,11,134 Retention of stereochemistry is also observed in the acid cleavage of phosphetanic amides into phosphetanic chlorides. 11,135 The stereochemical outcome can be explained as follows.…”

Section: Stereochemistry Of the Nucleophilic Substitutions On Phosphementioning

confidence: 98%

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Synthesis and Properties of Phosphetanes

Marinetti

Carmichael

2002

Chem. Rev.

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Section: The Mcbride Synthesis and Related Methodsmentioning

confidence: 99%

Section: Stereochemistry Of the Nucleophilic Substitutions On Phosphementioning

confidence: 98%

Synthesis and Properties of Phosphetanes

Marinetti

Carmichael

2002

Chem. Rev.

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“…Other representatives of this class of compound have since been described,2a,b'd,f and in several preliminary communicationsld we have described an approach to the synthesis of nonclassical thiophenes based upon the cycloaddition reactions of mesoionic ring systems6 with dibenzoylacetylene. The full de- technic Institute, 1973;(c) Sterling-Winthrop Fellow, 1971-1973 (d) preliminary communications: K. T. Potts and D. McKeough, J. Amer. Chem.…”

Section: Synthesis Of Nonclassical Thiophenes1mentioning

confidence: 99%

Photolysis of 1-azido-2,2,3,4,4-pentamethylphosphetane 1-oxide. Monomeric metaphosphonimidate

Wiseman¹,

Westheimer²

1974

J. Am. Chem. Soc.

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Monomeric metaphosphorimidates, 0=P(0R)=NR', have been postulated as reactive intermediates in phosphorus chemistry. Stereochemical evidence for such intermediates has now been obtained by photolysis, in methanol, of cis-and rra/u-l-azido-2,2,3,4,4-pemamethylphosphetane 1-oxide to yield the cis-and trans-2-methoxy-3,3,4,5,5-pentamethyl-l,2-azaphospholidene 2-oxides and eight other products. The starting materials and products have been separated and purified by high-pressure liquid chromatography, and their stereochemistry was established through their nmr spectra. The formation of the principal products has been rationalized on the assumption that photolysis of the azides leads to ring expansion with insertion of a nitrogen atom into the ring to yield a monomeric metaphosphonimidate, or with insertion of an oxygen atom into the ring to yield a new type of chemical intermediate. Consistent with this explanation, the ratio of cis-to fra/w-methyl phostamates, obtained as products of photolysis, is essentially independent of whether cis or trans azide is used as starting material. The chemistry and stereochemistry of monomeric metaphosphorimidates are discussed on the basis of these findings. The other products have also been accounted for, in most cases by assuming that a nitrene, or incipient nitrene, is formed in the photolysis.

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“…The ring constraints in this system provide a structural asset for the analysis of P stereochemistry, particularly where pseudorotational processes are involved (Westheimer, 1968). A ring methyl substituent cis or trans to a functional group provides a convenient probe to enable the following stereochemical changes (retention and inversion) about the P atom in chemical reactions (TrippeR, 1970(TrippeR, -1976Cremer & Trivedi, 1969). X-ray studies have provided confirmation of stereochemical assignments and important data on a number of pqaosphetane derivatives (Swank & Caughlan, 1968;Moret & Trefonas, 1969;Mazhar-ul-Haque, 1970, © 1979 International Union of Crystallography 1971; Mazhar-ul-Haque, Rashid & Cremer, 1978;Fitzgerald, Campbell, Smith, Caughlan & Cremer, 1978).…”

Section: Introductionmentioning

confidence: 99%

The crystal and molecular structure of 3,3-dimethyl-1,1-diphenylphosphetanium iodide

Mazhar-ul-Haque¹

1979

Acta Crystallogr Sect B

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Stereochemistry of nucleophilic attack on a cyclic phosphinate ester

Cited by 20 publications

References 0 publications

Synthesis and Properties of Phosphetanes

Synthesis and Properties of Phosphetanes

Photolysis of 1-azido-2,2,3,4,4-pentamethylphosphetane 1-oxide. Monomeric metaphosphonimidate

The crystal and molecular structure of 3,3-dimethyl-1,1-diphenylphosphetanium iodide

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