Two-directional elaboration of hydroxyacetone under thermodynamically controlled conditions

Allylation or 2-propynylation and aldol reaction

Teruhiko Ishikawa, Toshiaki Aikawa, Eiko Ohata, Takako Iseki, Satoshi Maeda, Takashi Matsuo, Tatsuo Fujino, Seiki Saito

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Enolate generated from O-(tetrahydropyran-2-yl)hydroxyacetone under thermodynamically controlled conditions (1.3 equiv of NaH, THF, 0 °C to rt) was allylated at the carbon bearing the protected hydroxy group with very high regioselectively. When tert-BuOH, equivalent to the excessive portion of initially added NaH, was introduced into the mixture followed by addition of aldehyde, aldol reaction took place on the methyl group to give 1-substituted 4-hydroxy-(1E),6-heptadien-3-one in acceptable yields after acidic treatment of the mixture for dehydration and deprotection. Introducing a chiral auxiliary protecting group into hydroxyacetone led to asymmetric allylation though stereoselectivity was around 50% ee. Thus, the hidden aspect of the chemoselective nature of protected hydroxy acetone-derived enolate generated under thermodynamically controlled conditions has opened a new avenue for two-directional elaboration of hydroxyacetone that should be potentially useful in organic synthesis.

Original languageEnglish
Pages (from-to)435-441
Number of pages7
JournalJournal of Organic Chemistry
Volume72
Issue number2
DOIs
Publication statusPublished - Jan 19 2007

Fingerprint

Allylation
Bearings (structural)
Stereoselectivity
Acetone
Dehydration
Aldehydes
Carbon
acetol
3-hydroxybutanal

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Two-directional elaboration of hydroxyacetone under thermodynamically controlled conditions : Allylation or 2-propynylation and aldol reaction. / Ishikawa, Teruhiko; Aikawa, Toshiaki; Ohata, Eiko; Iseki, Takako; Maeda, Satoshi; Matsuo, Takashi; Fujino, Tatsuo; Saito, Seiki.

In: Journal of Organic Chemistry, Vol. 72, No. 2, 19.01.2007, p. 435-441.

Research output: Contribution to journalArticle

Ishikawa, Teruhiko ; Aikawa, Toshiaki ; Ohata, Eiko ; Iseki, Takako ; Maeda, Satoshi ; Matsuo, Takashi ; Fujino, Tatsuo ; Saito, Seiki. / Two-directional elaboration of hydroxyacetone under thermodynamically controlled conditions : Allylation or 2-propynylation and aldol reaction. In: Journal of Organic Chemistry. 2007 ; Vol. 72, No. 2. pp. 435-441.
@article{caf5c1adc40a44b1b969fc943ddc367d,
title = "Two-directional elaboration of hydroxyacetone under thermodynamically controlled conditions: Allylation or 2-propynylation and aldol reaction",
abstract = "Enolate generated from O-(tetrahydropyran-2-yl)hydroxyacetone under thermodynamically controlled conditions (1.3 equiv of NaH, THF, 0 °C to rt) was allylated at the carbon bearing the protected hydroxy group with very high regioselectively. When tert-BuOH, equivalent to the excessive portion of initially added NaH, was introduced into the mixture followed by addition of aldehyde, aldol reaction took place on the methyl group to give 1-substituted 4-hydroxy-(1E),6-heptadien-3-one in acceptable yields after acidic treatment of the mixture for dehydration and deprotection. Introducing a chiral auxiliary protecting group into hydroxyacetone led to asymmetric allylation though stereoselectivity was around 50{\%} ee. Thus, the hidden aspect of the chemoselective nature of protected hydroxy acetone-derived enolate generated under thermodynamically controlled conditions has opened a new avenue for two-directional elaboration of hydroxyacetone that should be potentially useful in organic synthesis.",
author = "Teruhiko Ishikawa and Toshiaki Aikawa and Eiko Ohata and Takako Iseki and Satoshi Maeda and Takashi Matsuo and Tatsuo Fujino and Seiki Saito",
year = "2007",
month = "1",
day = "19",
doi = "10.1021/jo0618573",
language = "English",
volume = "72",
pages = "435--441",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Two-directional elaboration of hydroxyacetone under thermodynamically controlled conditions

T2 - Allylation or 2-propynylation and aldol reaction

AU - Ishikawa, Teruhiko

AU - Aikawa, Toshiaki

AU - Ohata, Eiko

AU - Iseki, Takako

AU - Maeda, Satoshi

AU - Matsuo, Takashi

AU - Fujino, Tatsuo

AU - Saito, Seiki

PY - 2007/1/19

Y1 - 2007/1/19

N2 - Enolate generated from O-(tetrahydropyran-2-yl)hydroxyacetone under thermodynamically controlled conditions (1.3 equiv of NaH, THF, 0 °C to rt) was allylated at the carbon bearing the protected hydroxy group with very high regioselectively. When tert-BuOH, equivalent to the excessive portion of initially added NaH, was introduced into the mixture followed by addition of aldehyde, aldol reaction took place on the methyl group to give 1-substituted 4-hydroxy-(1E),6-heptadien-3-one in acceptable yields after acidic treatment of the mixture for dehydration and deprotection. Introducing a chiral auxiliary protecting group into hydroxyacetone led to asymmetric allylation though stereoselectivity was around 50% ee. Thus, the hidden aspect of the chemoselective nature of protected hydroxy acetone-derived enolate generated under thermodynamically controlled conditions has opened a new avenue for two-directional elaboration of hydroxyacetone that should be potentially useful in organic synthesis.

AB - Enolate generated from O-(tetrahydropyran-2-yl)hydroxyacetone under thermodynamically controlled conditions (1.3 equiv of NaH, THF, 0 °C to rt) was allylated at the carbon bearing the protected hydroxy group with very high regioselectively. When tert-BuOH, equivalent to the excessive portion of initially added NaH, was introduced into the mixture followed by addition of aldehyde, aldol reaction took place on the methyl group to give 1-substituted 4-hydroxy-(1E),6-heptadien-3-one in acceptable yields after acidic treatment of the mixture for dehydration and deprotection. Introducing a chiral auxiliary protecting group into hydroxyacetone led to asymmetric allylation though stereoselectivity was around 50% ee. Thus, the hidden aspect of the chemoselective nature of protected hydroxy acetone-derived enolate generated under thermodynamically controlled conditions has opened a new avenue for two-directional elaboration of hydroxyacetone that should be potentially useful in organic synthesis.

UR - http://www.scopus.com/inward/record.url?scp=33846217034&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33846217034&partnerID=8YFLogxK

U2 - 10.1021/jo0618573

DO - 10.1021/jo0618573

M3 - Article

VL - 72

SP - 435

EP - 441

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 2

ER -