TY - JOUR
T1 - Rhodium-catalyzed transformation of propargyl alcohol derivatives to 2-silylmethyl-2-alkenals
AU - Matsuda, Isamu
AU - Niikawa, Nakayoshi
AU - Kuwabara, Rika
AU - Inoue, Hirofumi
AU - Nagashima, Hideo
AU - Itoh, Kenji
N1 - Funding Information:
This work was supported by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, and Culture, Japan and Ciba-Geigy Foundation (Japan) for the Promotion of Science.
PY - 1999/2/8
Y1 - 1999/2/8
N2 - Propargyl-type alcohols (6) and the corresponding esters of carbonic acid (4) or acetic acid (5) react with two equivalents of Me2PhSiH in the presence of catalytic amounts of Rh4(CO)12 under CO pressure at 100°C to give 2-(dimethylphenylsilylmethyl)-2-alkenals (3), whereas 2-substituted-3-(dimethylphenylsilyl)propenals (7, 8 and 9) are also isolated with the concomitant formation of 3 when a similar reaction is operated with shortage of Me2PhSiH or with lowering of reaction temperature. The isolated 9 is selectively converted to 3 by the Rh4(CO)12 catalyzed reaction with Me2PhSiH under CO pressure. This fact suggests that the transformation of 4, 5 or 6 to 3 is accomplished by either a one-pot procedure or a stepwise procedure relayed by 7, 8 or 9. Usefulness of this protocol is demonstrated by the synthesis of 18 in which ethisterone (17) is directly converted by a one-pot procedure.
AB - Propargyl-type alcohols (6) and the corresponding esters of carbonic acid (4) or acetic acid (5) react with two equivalents of Me2PhSiH in the presence of catalytic amounts of Rh4(CO)12 under CO pressure at 100°C to give 2-(dimethylphenylsilylmethyl)-2-alkenals (3), whereas 2-substituted-3-(dimethylphenylsilyl)propenals (7, 8 and 9) are also isolated with the concomitant formation of 3 when a similar reaction is operated with shortage of Me2PhSiH or with lowering of reaction temperature. The isolated 9 is selectively converted to 3 by the Rh4(CO)12 catalyzed reaction with Me2PhSiH under CO pressure. This fact suggests that the transformation of 4, 5 or 6 to 3 is accomplished by either a one-pot procedure or a stepwise procedure relayed by 7, 8 or 9. Usefulness of this protocol is demonstrated by the synthesis of 18 in which ethisterone (17) is directly converted by a one-pot procedure.
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U2 - 10.1016/S0022-328X(98)00933-4
DO - 10.1016/S0022-328X(98)00933-4
M3 - Article
AN - SCOPUS:0001396021
SN - 0022-328X
VL - 574
SP - 133
EP - 141
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1
ER -