Electrogenerated acid-catalyzed reactions of acetals, aldehydes, and ketones with organosilicon compounds, leading to aldol reactions, allylations, cyanations, and hydride additions.
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概要
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Exquisite use of electrogenerated acid (EG acid) in the silicon-mediated acid-catalyzed reactions; e.g., aldol reactions, allylations, cyanations, and hydride additions is described. The aldol reaction of acetals <B>1</B> with enol trimethylsilyl ethers <B>3</B> and 1,2-bis(trimethylsiloxy)alkenes <B>4</B> gives the corresponding adducts <B>5</B> and <B>6</B>, respectively. The reaction proceeds smoothly with EG acid derived from perchlorate salts such as LiClO<SUB>4</SUB>, <I>n</I>-Bu<SUB>4</SUB>NClO<SUB>4</SUB>, and Mg(ClO<SUB>4</SUB>)<SUB>2</SUB> in dichloromethane using platinum electrodes. The amount of electricity required to complete the reaction implies a cationic process which is mediated by the trimethylsilyl moiety. This aldol reaction is further developed with unprotected carbonyl compounds <B>2</B> with <B>3</B>, giving the trimethylsilyl ethers of the adducts <B>7</B>. Further utility of this EG acid as a catalyst for a chain reaction is exemplified by the successful application in the following conversions: (1) The allylation of acetals <B>1</B> with allyltrimethylsilane (<B>8</B>) to give <B>9</B>, (2) the cyanation of acetals <B>1</B> and unmasked <B>2</B> with trimethylsilyl cyanide (<B>10</B>) to give <B>11</B>, <B>12</B>, and <B>13</B>, and (3) the hydride addition of acetals <B>1</B> with triethylsilane (<B>14</B>) to give <B>15</B>.
- 公益社団法人 日本化学会の論文
著者
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Torii Sigeru
Department Of Applied Chemistry Faculty Of Engineering Okayama University
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Inokuchi Tsutomu
Department Of Applied Chemistry Faculty Of Engineering Okayama University
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Uneyama Kenji
Department Of Applied Chemistry Faculty Of Engineering Okayama University
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Kuroda Hideki
Department Of Gynecology And Obstetrics Faculty Of Medicine Kyoto University
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Horike Hirofumi
Department of Alzheimer's Disease Research, Research Institute, National Center for Geriatrics and Gerontology (NCGG)
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Takagishi Sadahito
Department of Industrial Chemistry, School of Engineering, Okayama University
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