‘Reductive ozonolysis’ via a new fragmentation of carbonyl oxides

Schwartz, Chris; Raible, Joseph; Mott, Kyle; Dussault, Patrick H.

doi:10.1016/j.tet.2006.08.092

Cited by 33 publications

(28 citation statements)

References 39 publications

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“…However, some oxidative transformations proved to be more problematic. After treatment of the allyl trisphosphonate 11 with ozone under typical conditions 11 some evidence for formation of the desired aldehyde 17 was obtained, including a resonance appropriate for the aldehyde hydrogen in the 1 H NMR spectrum. However, this material was obtained in low yield and there was detectable dephosphorylation to a bisphosphonate.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Reactivity of Alkyl-1,1,1-trisphosphonate Esters

Smits

Wiemer

2011

J. Org. Chem.

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The α–trisphosphonic acid esters provide a unique spatial arrangement of three phosphonate groups, and may represent an attractive motif for inhibitors of enzymes that utilize di- or triphosphate substrates. To advance studies of this unique functionality, a general route to alkyl derivatives of the parent system (R = H) has been developed. A set of new α-alkyl-1,1,1-trisphosphonate esters has been prepared through phosphinylation and subsequent oxidation of tetraethyl alkylbisphosphonates, and the reactivity of these new compounds has been studied in representative reactions that afford additional examples of this functionality.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Reactivity of Alkyl-1,1,1-trisphosphonate Esters

Smits

Wiemer

2011

J. Org. Chem.

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“…4 We have recently reported several methods for “reductive” ozonolysis that directly generate carbonyl products, avoiding formation of isolable peroxides. 5a–c We now report the successful application of reductive ozonolyses in tandem with a number of the most common methods for carbon-carbon bond-forming reactions.…”

Section: Introductionmentioning

confidence: 99%

“…The first (Scheme 2, path a) involves an operationally simple protocol, ozonolysis in wet acetonitrile or wet acetone. 5b In this case, attack of solubilized water on the carbonyl oxide generates a tetrahedral intermediate that decomposes to furnish the carbonyl product(s) and hydrogen peroxide. The second (Scheme 2, path b) involves ozonolysis in the presence of N -methyl morpholine N -oxide (NMMO) or related N -oxides.…”

Section: Introductionmentioning

confidence: 99%

Tandem Application of C–C Bond-Forming Reactions with Reductive Ozonolysis

Willand‐Charnley

Dussault

2012

J. Org. Chem.

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Several variants of reductive ozonolysis, defined here as the in situ generation of aldehydes or ketones during ozonolytic cleavage of alkenes, are demonstrated to work effectively in tandem with a number of C-C bond-forming reactions. For reactions involving basic nucleophiles (1,2-addition of Grignard reagents, Wittig or Horner-Emmons olefinations, and directed Aldol reactions of lithium enolates) the one-pot process offers a rapid and high-yielding alternative to traditional two-step protocols.

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“…In the course of investigations into the addition of oxygen nucleophiles to ozonolysis-derived carbonyl oxides,6 we observed the rapid dehydration of secondary hydroperoxyacetals in the presence of commercial bleach 7. We now report that Ca(OCl) 2 , t -BuOCl, and trichloroisocyanuric acid mediate the rapid heterolytic dehydration of hydroperoxyacetals through the apparent intermediacy of secondary chloroperoxides, species whose solution chemistry has not been previously described.…”

Section: Introductionmentioning

confidence: 99%