TY - JOUR
T1 - Stereoselectivity of the Rearrangement of Allyl Siloxyvinyl Ethers. A Highly Stereoselective Synthesis of a Diol Found in the Pheromonal Secretion of the Queen Butterfly
AU - Katzenellenbogen, John A.
AU - Christy, Kenneth J.
PY - 1974/11/1
Y1 - 1974/11/1
N2 - The [3,3] rearrangement of 3-acetoxy-2-methyl-1-nonene (1b), derivatized as the trimethylsiloxyvinyl ether, proceeds in moderate yield (ca. 53%) but with very high stereoselectivity (>98%) to give the β,γ-unsaturated acid 2a. Rearrangement of the tert-butyldimethylsiloxyvinyl ether derivative proceeds in higher yield (80%), also with very high stereoselectivity. This rearrangement has been used in a stereoselective synthesis of a terpenoid diol (8) found in the phermonal secretion of the queen butterfly, in six steps from geraniol.
AB - The [3,3] rearrangement of 3-acetoxy-2-methyl-1-nonene (1b), derivatized as the trimethylsiloxyvinyl ether, proceeds in moderate yield (ca. 53%) but with very high stereoselectivity (>98%) to give the β,γ-unsaturated acid 2a. Rearrangement of the tert-butyldimethylsiloxyvinyl ether derivative proceeds in higher yield (80%), also with very high stereoselectivity. This rearrangement has been used in a stereoselective synthesis of a terpenoid diol (8) found in the phermonal secretion of the queen butterfly, in six steps from geraniol.
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U2 - 10.1021/jo00937a002
DO - 10.1021/jo00937a002
M3 - Article
AN - SCOPUS:0038210999
SN - 0022-3263
VL - 39
SP - 3315
EP - 3318
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 23
ER -