Abstract
Virtually complete asymmetric induction is achieved during methyl-, vinyl-, and naphthylmetallic conjugate addition to enantiomerically pure (S)-(+)-2-(p-tolylsulfinyl)-2-cyclopentenone ((S)-(+)-1). (R)-3-Methylcyclopentanone is obtained when the enone sulfoxide (S)-(+)-1 is first complexed with divalent zinc and then methylmagnesium iodide is added, whereas (S)-3-methylcyclopentanone is obtained when methylmagnesium iodide is added to the same, uncomplexed enone sulfoxide. (R)-3-Methylcyclopentanone is obtained also when the enone sulfoxide is treated separately with lithium tetramethylaluminate, methyltitanium triisopropoxide, and methylmagnesium chloride. (S)-(+)-2-(1-Naphthylsulfinyl)-2-cyclopentenone ((S)-(+)-1′) gives mainly the unexpected (S)-3-methylcyclopentanone on reaction with dimethylcopperlithium. Enantiomerically pure steroid intermediates (S,S)-(+)-4 and (S,S)-(+)-7 are prepared in short, convergent, and high-yield sequences starting with enone sulfoxide (S)-(+)-1.
| Original language | English |
|---|---|
| Pages (from-to) | 4180-4185 |
| Number of pages | 6 |
| Journal | Journal of the American Chemical Society |
| Volume | 104 |
| Issue number | 15 |
| State | Published - 1982 |
| Externally published | Yes |
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All Science Journal Classification (ASJC) codes
- Chemistry(all)
Cite this
Asymmetric induction during organometallic conjugate addition to enantiomerically pure 2-(arylsulfinyl)-2-cyclopentenones. / Posner, Gary H.; Mallamo, John P.; Hulce, Martin; Frye, Leah L.
In: Journal of the American Chemical Society, Vol. 104, No. 15, 1982, p. 4180-4185.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Asymmetric induction during organometallic conjugate addition to enantiomerically pure 2-(arylsulfinyl)-2-cyclopentenones
AU - Posner, Gary H.
AU - Mallamo, John P.
AU - Hulce, Martin
AU - Frye, Leah L.
PY - 1982
Y1 - 1982
N2 - Virtually complete asymmetric induction is achieved during methyl-, vinyl-, and naphthylmetallic conjugate addition to enantiomerically pure (S)-(+)-2-(p-tolylsulfinyl)-2-cyclopentenone ((S)-(+)-1). (R)-3-Methylcyclopentanone is obtained when the enone sulfoxide (S)-(+)-1 is first complexed with divalent zinc and then methylmagnesium iodide is added, whereas (S)-3-methylcyclopentanone is obtained when methylmagnesium iodide is added to the same, uncomplexed enone sulfoxide. (R)-3-Methylcyclopentanone is obtained also when the enone sulfoxide is treated separately with lithium tetramethylaluminate, methyltitanium triisopropoxide, and methylmagnesium chloride. (S)-(+)-2-(1-Naphthylsulfinyl)-2-cyclopentenone ((S)-(+)-1′) gives mainly the unexpected (S)-3-methylcyclopentanone on reaction with dimethylcopperlithium. Enantiomerically pure steroid intermediates (S,S)-(+)-4 and (S,S)-(+)-7 are prepared in short, convergent, and high-yield sequences starting with enone sulfoxide (S)-(+)-1.
AB - Virtually complete asymmetric induction is achieved during methyl-, vinyl-, and naphthylmetallic conjugate addition to enantiomerically pure (S)-(+)-2-(p-tolylsulfinyl)-2-cyclopentenone ((S)-(+)-1). (R)-3-Methylcyclopentanone is obtained when the enone sulfoxide (S)-(+)-1 is first complexed with divalent zinc and then methylmagnesium iodide is added, whereas (S)-3-methylcyclopentanone is obtained when methylmagnesium iodide is added to the same, uncomplexed enone sulfoxide. (R)-3-Methylcyclopentanone is obtained also when the enone sulfoxide is treated separately with lithium tetramethylaluminate, methyltitanium triisopropoxide, and methylmagnesium chloride. (S)-(+)-2-(1-Naphthylsulfinyl)-2-cyclopentenone ((S)-(+)-1′) gives mainly the unexpected (S)-3-methylcyclopentanone on reaction with dimethylcopperlithium. Enantiomerically pure steroid intermediates (S,S)-(+)-4 and (S,S)-(+)-7 are prepared in short, convergent, and high-yield sequences starting with enone sulfoxide (S)-(+)-1.
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M3 - Article
AN - SCOPUS:33845553289
VL - 104
SP - 4180
EP - 4185
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 15
ER -