Novel Rearrangements of the 2-Chloroacrylonitrile Cycloadducts of Steroidal 14,16-Dien-17-yl Acetates

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Title:Novel Rearrangements of the 2-Chloroacrylonitrile Cycloadducts of Steroidal 14,16-Dien-17-yl Acetates
Creators:
Bull, James R.
Gordon, Richard S.
Grundler, Claudia
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 66, 12, pp. 1777-1796
Uncontrolled Keywords:Rearrangements, [4 + 2]Cycloadditions, Steroids, 2-Chloroacrylonitrile, 19-Norsteroids, Estradiols

Abstract

Cycloaddition of 3-methoxyestra-1,3,5(10),14,16-pentaen-17-yl acetate (<strong>1</strong>) with 2-chloroacrylonitrile furnishes 17β-acetoxy-16α-chloro-3-methoxy-14,17α-ethenoestra-1,3,5(10)-triene-16β-carbonitrile (<strong>2</strong>) as the major product, which undergoes alkali-mediated rearrangement to (16<sup>1</sup><i>R</i>)-3-methoxy-17-oxo-16β,15β,14-(ethane[1,1,2]triyl)-14β-estra-1,3,5(10)-triene-16<sup>1</sup>-carbonitrile (<strong>7</strong>). A similar reaction course is followed by the related 16-methyl derivative <strong>4</strong>, and it is shown that minor 15-chloro-15-cyano cycloadducts <strong>3</strong> and <strong>6</strong> undergo Grob fragmentation. Functional group manipulations and regioselective bond-scission processes are described, for conversion of rearrangement product <strong>7</strong> into 16β,15β,14-(ethane[1,1,2]triyl) and cyclobuta[14β,15β] analogues of estradiol. <p>

Title:Novel Rearrangements of the 2-Chloroacrylonitrile Cycloadducts of Steroidal 14,16-Dien-17-yl Acetates
Creators:
Bull, James R.
Gordon, Richard S.
Grundler, Claudia
Uncontrolled Keywords:Rearrangements, [4 + 2]Cycloadditions, Steroids, 2-Chloroacrylonitrile, 19-Norsteroids, Estradiols
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:66
Number:12
Page Range:pp. 1777-1796
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20011777UNSPECIFIED
ID Code:1895
Item Type:Article
Deposited On:06 Feb 2009 17:13
Last Modified:06 Feb 2009 16:13

Citation

Bull, James R.; Gordon, Richard S.; Grundler, Claudia (2001) Novel Rearrangements of the 2-Chloroacrylonitrile Cycloadducts of Steroidal 14,16-Dien-17-yl Acetates. Collection of Czechoslovak Chemical Communications, 66 (12). pp. 1777-1796. ISSN 0010-0765

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