Highly stereoselective addition of silylphosphines to chiral aldehydes

Kolodiazhnyi, Oleg I.; Guliaiko, Irina V.; Kolodiazhna, Anastasy O.

doi:10.1016/j.tetlet.2004.07.074

Cited by 27 publications

(15 citation statements)

References 7 publications

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“…R = R´ = Ph (6,9,12); R = Ph, R´ = Et (7, 10, 13); R = 4 Me 2 NC 6 H 4 , R´ = OCH 2 CH 2 Cl (8,11,14) Due to the presence of the enantiomerically pure men thol fragment in molecules 3-5, 10, and 11, the reac tions produce mixtures of two diastereomers, which differ in the configuration of the chiral center at the phosphorus atom. The ratios of diastereomers were determined based on the integral intensities of the signals for the phospho rus atoms in the 31 P NMR spectra (see the Experimental section).…”

Section: Methodsmentioning

confidence: 99%

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Nonracemic menthyl phosphorylacetates

et al. 2007

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Section: Methodsmentioning

confidence: 99%

“…9 Samples substantially enriched in one of diastereomers were obtained by column chroma tography and fractional crystallization. Apparently, higher stereoselectivity of these re actions is favored by the steric and electronic effects of the aryl substituent.…”

Section: Methodsmentioning

confidence: 99%

Nonracemic menthyl phosphorylacetates

et al. 2007

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“…Silylphosphines have substantially nucleophilic nature though they are sterically protected by the silyl group (vide supra). Indeed, relatively small or highly reactive electrophiles, such as enones,26 alkynyl ketones,24,27 and non‐hindered aldehydes,28,29 smoothly reacted without any activation to give the corresponding adducts (α‐silyloxyalkylphosphines: 1,2‐adduct for aldehydes; β‐phosphinoketones: 1,4‐adduct for enones and alkynyl ketones). However, silylphosphines generally showed very low reactivity toward other electrophiles such as ketones and alkyl halides.…”

Section: Nucleophilic Activation Of Silylphosphinesmentioning

confidence: 99%

Organophosphine syntheses via activation of the phosphorus‐silicon bond of silylphosphines

Hayashi

2009

The Chemical Record

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This paper describes the recent advances in the syntheses of organophosphines by forming several types of phosphorus-carbon bonds via activation of the phosphorus-silicon bond of silylphosphines. In this account, the activation methods are classified into three types: nucleophile-induced activations, reactions with Lewis acid-activated electrophiles, and transition metal catalyzed reactions. Nucleophile-induced activations of silylphosphines, especially by a fluoride, generated a reactive phosphide equivalent for selective formation of a P-C bond. Silylphosphines also reacted selectively with Lewis acid-activated electrophiles. The Lewis acid mediated/catalyzed additions and substitutions, to form sp3-carbon-phosphorus bonds including an asymmetric reaction, are described. Several important types of transition metal catalyzed reactions of silylphosphines are also mentioned in this account. Selective formation of a P-C bond is achieved through these activations to produce a variety of functional organophosphines including optically active ones.

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“…Several representative reactions are shown in Scheme to illustrate the utility of phosphines with P‐Si functionalities. Phosphines with a single trimethylsilyl substituent may be employed to functionalize alkenes and alkynes A 6–12, ring‐open epoxides B 13, add to aldehydes C 13–15, and support metal‐catalyzed coupling reactions D 16–18. In addition, bis(trimethylsilyl)phosphines are important precursors to diphosphenes E 19, and phosphaalkenes F 20 when appropriately bulky aryl substituents (Ar) are employed.…”

Section: Introductionmentioning

confidence: 99%