Fischer Indole Synthesis with Selected 2,3-Dideoxy-D-glycero-aldopentose Derivatives. Conversion of D-Xylose to (2S)-3-(Indol-3-yl)propane-1,2-diol

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Title:Fischer Indole Synthesis with Selected 2,3-Dideoxy-D-glycero-aldopentose Derivatives. Conversion of D-Xylose to (2S)-3-(Indol-3-yl)propane-1,2-diol
Creators:
Lajšic, Stevan
Cetkovic, Gordana
Popsavin, Mirjana
Popsavin, Velimir
Miljković, Dušan
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 61, 2, pp. 298-304
Uncontrolled Keywords:D-Xylose, Dethioacetalation, Fischer indol synthesis, Ethanethiolysis

Abstract

Two independent routes towards (2<i>S</i>)-3-(indol-3-yl)propane-1,2-diol (<strong>11</strong>) were achieved starting from 3,5-di-<i>O</i>-acetyl-1,2-<i>O</i>-cyclohexylidene-α-D-xylofuranose (<strong>1</strong>). Ethanethiolysis of <strong>1</strong> afforded acyclic diethyl dithioacetal <strong>2</strong> which was further <i>O</i>-deacetylated to give <strong>3</strong>. Selective benzoylation of <strong>3</strong> gave 5-<i>O</i>-benzoyl derivative <strong>4</strong>. Treatment of <strong>4</strong> with <i>N</i>-bromosuccinimide in methanol gave methyl furanoside <strong>5</strong> which was further desulfurized over Raney nickel to afford <strong>6</strong>. An acid hydrolysis of <strong>6</strong> gave hemiacetal <strong>7</strong> which upon treatment with phenylhydrazine, according to standard Fischer indolization procedure, yielded a mixture of chiral indoles <strong>10</strong>. <i>O</i>-Debenzoylation of <strong>10</strong> gave the crystalline diol <strong>11</strong>. A more efficient route towards the chiral indole <strong>11</strong> included the initial dethioacetalation of <strong>2</strong> into dimethyl acetal <strong>8</strong> which was further desulfurized over Raney nickel to give the corresponding 2,3-dideoxy derivative <strong>9</strong>. Direct Fischer indolization of <strong>9</strong> with phenylhydrazine, followed by <i>O</i>-deacetylation of intermediate <strong>12</strong>, afforded the expected indole <strong>11</strong> in good yield. <br />

Title:Fischer Indole Synthesis with Selected 2,3-Dideoxy-D-glycero-aldopentose Derivatives. Conversion of D-Xylose to (2S)-3-(Indol-3-yl)propane-1,2-diol
Creators:
Lajšic, Stevan
Cetkovic, Gordana
Popsavin, Mirjana
Popsavin, Velimir
Miljković, Dušan
Uncontrolled Keywords:D-Xylose, Dethioacetalation, Fischer indol synthesis, Ethanethiolysis
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:61
Number:2
Page Range:pp. 298-304
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19960298UNSPECIFIED
ID Code:932
Item Type:Article
Deposited On:06 Feb 2009 17:05
Last Modified:06 Feb 2009 16:05

Citation

Lajšic, Stevan; Cetkovic, Gordana; Popsavin, Mirjana; Popsavin, Velimir; Miljković, Dušan (1996) Fischer Indole Synthesis with Selected 2,3-Dideoxy-D-glycero-aldopentose Derivatives. Conversion of D-Xylose to (2S)-3-(Indol-3-yl)propane-1,2-diol. Collection of Czechoslovak Chemical Communications, 61 (2). pp. 298-304. ISSN 0010-0765

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