An efficient generation of the aluminum enolates of 1H-perfluoroalkyl ketones from 1-substituted-1-perfluoroalkenyl phosphates and their aldol reaction with aldehydes

Takashi Ishihara, Manabu Kuroboshi, Koichi Yamaguchi, Yoshiji Okada

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

Diethyl 1-substituted-1-perfluoroalkenyl phosphates (1), available from perfluoroalkyl ketones and sodium diethyl phosphite, were allowed to react with a reagent derived from lithium aluminum hydride and a metal salt or bromine in tetrahydrofuran below -30°C and successively treated with water or aldehydes to give rise to the corresponding 1H-perfluoroalkyl ketones (4) or α-fluoro-α-perfluoroalkyl-β-hydroxy ketones (5), respectively, in moderate to good yields. Copper(II) bromide, copper(I) bromide, and zinc chloride could be employed as the metal salt in the reaction. The phosphates also underwent reductive dephosphorylation with diisobutylaluminum hydride to generate the aluminum enolates of 1H-perfluoroalkyl ketones. 19F NMR analyses indicated that their structure is not an α-metallo ketone but an oxygen-metalated species and that they are appreciably stable below 0°C. Treatment with a wide variety of aldehydes at 0°C yielded the corresponding aldol products 5 in good to excellent yields, whereas ketones did not react.

Original languageEnglish
Pages (from-to)3107-3114
Number of pages8
JournalJournal of Organic Chemistry
Volume55
Issue number10
Publication statusPublished - 1990
Externally publishedYes

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Ketones
Aluminum
Aldehydes
Phosphates
Salts
Metals
Phosphites
Bromine
3-hydroxybutanal
Copper
Sodium
Nuclear magnetic resonance
Oxygen
Water

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

An efficient generation of the aluminum enolates of 1H-perfluoroalkyl ketones from 1-substituted-1-perfluoroalkenyl phosphates and their aldol reaction with aldehydes. / Ishihara, Takashi; Kuroboshi, Manabu; Yamaguchi, Koichi; Okada, Yoshiji.

In: Journal of Organic Chemistry, Vol. 55, No. 10, 1990, p. 3107-3114.

Research output: Contribution to journalArticle

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abstract = "Diethyl 1-substituted-1-perfluoroalkenyl phosphates (1), available from perfluoroalkyl ketones and sodium diethyl phosphite, were allowed to react with a reagent derived from lithium aluminum hydride and a metal salt or bromine in tetrahydrofuran below -30°C and successively treated with water or aldehydes to give rise to the corresponding 1H-perfluoroalkyl ketones (4) or α-fluoro-α-perfluoroalkyl-β-hydroxy ketones (5), respectively, in moderate to good yields. Copper(II) bromide, copper(I) bromide, and zinc chloride could be employed as the metal salt in the reaction. The phosphates also underwent reductive dephosphorylation with diisobutylaluminum hydride to generate the aluminum enolates of 1H-perfluoroalkyl ketones. 19F NMR analyses indicated that their structure is not an α-metallo ketone but an oxygen-metalated species and that they are appreciably stable below 0°C. Treatment with a wide variety of aldehydes at 0°C yielded the corresponding aldol products 5 in good to excellent yields, whereas ketones did not react.",
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AU - Ishihara, Takashi

AU - Kuroboshi, Manabu

AU - Yamaguchi, Koichi

AU - Okada, Yoshiji

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Y1 - 1990

N2 - Diethyl 1-substituted-1-perfluoroalkenyl phosphates (1), available from perfluoroalkyl ketones and sodium diethyl phosphite, were allowed to react with a reagent derived from lithium aluminum hydride and a metal salt or bromine in tetrahydrofuran below -30°C and successively treated with water or aldehydes to give rise to the corresponding 1H-perfluoroalkyl ketones (4) or α-fluoro-α-perfluoroalkyl-β-hydroxy ketones (5), respectively, in moderate to good yields. Copper(II) bromide, copper(I) bromide, and zinc chloride could be employed as the metal salt in the reaction. The phosphates also underwent reductive dephosphorylation with diisobutylaluminum hydride to generate the aluminum enolates of 1H-perfluoroalkyl ketones. 19F NMR analyses indicated that their structure is not an α-metallo ketone but an oxygen-metalated species and that they are appreciably stable below 0°C. Treatment with a wide variety of aldehydes at 0°C yielded the corresponding aldol products 5 in good to excellent yields, whereas ketones did not react.

AB - Diethyl 1-substituted-1-perfluoroalkenyl phosphates (1), available from perfluoroalkyl ketones and sodium diethyl phosphite, were allowed to react with a reagent derived from lithium aluminum hydride and a metal salt or bromine in tetrahydrofuran below -30°C and successively treated with water or aldehydes to give rise to the corresponding 1H-perfluoroalkyl ketones (4) or α-fluoro-α-perfluoroalkyl-β-hydroxy ketones (5), respectively, in moderate to good yields. Copper(II) bromide, copper(I) bromide, and zinc chloride could be employed as the metal salt in the reaction. The phosphates also underwent reductive dephosphorylation with diisobutylaluminum hydride to generate the aluminum enolates of 1H-perfluoroalkyl ketones. 19F NMR analyses indicated that their structure is not an α-metallo ketone but an oxygen-metalated species and that they are appreciably stable below 0°C. Treatment with a wide variety of aldehydes at 0°C yielded the corresponding aldol products 5 in good to excellent yields, whereas ketones did not react.

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