2003
DOI: 10.1021/jo026639y
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Dimethylmalonyltrialkylphosphoranes:  New General Reagents for Esterification Reactions Allowing Controlled Inversion or Retention of Configuration on Chiral Alcohols

Abstract: A new class of trialkylphosphorane has been prepared through reaction of a trialkylphosphine with 2-chlorodimethylmalonate in the presence of triethylamine. These new reagents promote the condensation reaction of carboxylic acids with alcohols to provide esters along with trialkylphosphine oxide and dimethylmalonate. The condensation reaction of chiral secondary alcohols can be controlled to give either high levels of inversion or retention through a subtle interplay involving basicity of the reaction media, s… Show more

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Cited by 52 publications
(29 citation statements)
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“…Dimethyl tributylphosphoranylidenemalonate (13, Figure 7) has been introduced by McNulty et al [64] and can be prepared in one step from trialkylphosphane and 2-chlorodimethylmalonate. With reagent 13 esterification of simple primary or secondary alcohols proceeds with a 70Ϫ98% yield.…”
Section: Alternative Reagentsmentioning
confidence: 99%
“…Dimethyl tributylphosphoranylidenemalonate (13, Figure 7) has been introduced by McNulty et al [64] and can be prepared in one step from trialkylphosphane and 2-chlorodimethylmalonate. With reagent 13 esterification of simple primary or secondary alcohols proceeds with a 70Ϫ98% yield.…”
Section: Alternative Reagentsmentioning
confidence: 99%
“…Other phosphorane reagents, most significantly TsunodaÕs cyanomethylene reagents, generate basic anions during the reaction and thus provide results similar to the original Mitsunobu class [10][11][12] In contrast, our recently [6] reported phosphorane, synthesized from tributylphosphine and chlorodimethylmalonate, produces an intermediate that expels the dimethylmalonyl anion and is therefore significantly less basic than 6. This tributylphosphorane reagent was shown to promote the general condensation reaction of a wide range of carboxylic acid and alcohol partners, through generation of intermediates analogous to 5 under conditions of controlled reaction basicity, providing esters along with tributylphosphine oxide and dimethylmalonate [6]. In addition to the levels of stereocontrol achievable (vide infra), the side products produced are easily removed by aqueous base partition, eliminating the purification difficulties inherent in the use of standard Mitsunobu reagents.…”
mentioning
confidence: 87%
“…However, in recent years several accounts reporting retention of stereochemistry have been disclosed [5][6][7][8] involving the condensation of sterically hindered secondary alcohols under standard Mitsunobu conditions. A somewhat modified view of the reaction mechanism has evolved outlined in Scheme 1.…”
mentioning
confidence: 99%
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