Abstract
Stereocontrolled asymmetric total synthesis of protomycinolide IV (1) was achieved, based on the organo-aluminum-promoted stereospecific pinacol-type 1,2-rearrangement. Two chiral fragments, C(1)–C(9) and C(11)–(17) portions, were constructed from a common chiral starting material, (S)-ethyl lactate. High diastereoselectivity of the nucleophilic attack on the Me3Si-bearing α-methyl-β,γ-unsaturated carbonyl compounds was fully utilized for establishing the chiral centers at C(5) and C(6) relative to C(4) and C(15) relative to C(14). For the stereocontrol of the Me substituent at C(8), two methods were newly devised: (i) thermodynamic equilibration of δ-lactone 16 and (ii) acid-catalyzed stereoselective cyclization of ketene dithioacetal possessing an internal hydroxyl group.
| Original language | English |
|---|---|
| Pages (from-to) | 5221-5229 |
| Number of pages | 9 |
| Journal | Journal of the American Chemical Society |
| Volume | 108 |
| Issue number | 17 |
| DOIs | |
| Publication status | Published - Jan 1 1986 |
| Externally published | Yes |
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All Science Journal Classification (ASJC) codes
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Stereocontrolled Asymmetric Total Synthesis of Protomycinolide IV. / Suzuki, Keisuke; Tomooka, Katsuhiko; Katayama, Eiji; Matsumoto, Takashi; Tsuchihashi, Gen ichi.
In: Journal of the American Chemical Society, Vol. 108, No. 17, 01.01.1986, p. 5221-5229.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Stereocontrolled Asymmetric Total Synthesis of Protomycinolide IV
AU - Suzuki, Keisuke
AU - Tomooka, Katsuhiko
AU - Katayama, Eiji
AU - Matsumoto, Takashi
AU - Tsuchihashi, Gen ichi
PY - 1986/1/1
Y1 - 1986/1/1
N2 - Stereocontrolled asymmetric total synthesis of protomycinolide IV (1) was achieved, based on the organo-aluminum-promoted stereospecific pinacol-type 1,2-rearrangement. Two chiral fragments, C(1)–C(9) and C(11)–(17) portions, were constructed from a common chiral starting material, (S)-ethyl lactate. High diastereoselectivity of the nucleophilic attack on the Me3Si-bearing α-methyl-β,γ-unsaturated carbonyl compounds was fully utilized for establishing the chiral centers at C(5) and C(6) relative to C(4) and C(15) relative to C(14). For the stereocontrol of the Me substituent at C(8), two methods were newly devised: (i) thermodynamic equilibration of δ-lactone 16 and (ii) acid-catalyzed stereoselective cyclization of ketene dithioacetal possessing an internal hydroxyl group.
AB - Stereocontrolled asymmetric total synthesis of protomycinolide IV (1) was achieved, based on the organo-aluminum-promoted stereospecific pinacol-type 1,2-rearrangement. Two chiral fragments, C(1)–C(9) and C(11)–(17) portions, were constructed from a common chiral starting material, (S)-ethyl lactate. High diastereoselectivity of the nucleophilic attack on the Me3Si-bearing α-methyl-β,γ-unsaturated carbonyl compounds was fully utilized for establishing the chiral centers at C(5) and C(6) relative to C(4) and C(15) relative to C(14). For the stereocontrol of the Me substituent at C(8), two methods were newly devised: (i) thermodynamic equilibration of δ-lactone 16 and (ii) acid-catalyzed stereoselective cyclization of ketene dithioacetal possessing an internal hydroxyl group.
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U2 - 10.1021/ja00277a028
DO - 10.1021/ja00277a028
M3 - Article
AN - SCOPUS:0022457825
VL - 108
SP - 5221
EP - 5229
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 17
ER -