Rhodium-catalyzed transformation of propargyl alcohol derivatives to 2-silylmethyl-2-alkenals

Isamu Matsuda, Nakayoshi Niikawa, Rika Kuwabara, Hirofumi Inoue, Hideo Nagashima, Kenji Itoh

Research output: Contribution to journalArticle

19 Citations (Scopus)

Abstract

Propargyl-type alcohols (6) and the corresponding esters of carbonic acid (4) or acetic acid (5) react with two equivalents of Me 2 PhSiH in the presence of catalytic amounts of Rh 4 (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 Me 2 PhSiH or with lowering of reaction temperature. The isolated 9 is selectively converted to 3 by the Rh 4 (CO) 12 catalyzed reaction with Me 2 PhSiH 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.

Original languageEnglish
Pages (from-to)133-141
Number of pages9
JournalJournal of Organometallic Chemistry
Volume574
Issue number1
DOIs
Publication statusPublished - Feb 8 1999
Externally publishedYes

Fingerprint

Rhodium
Carbon Monoxide
rhodium
alcohols
Alcohols
Derivatives
Acetic acid
carbonic acid
Ethisterone
Esters
Carbonic Acid
acetic acid
Pressure
Acids
esters
Acetic Acid
synthesis
Temperature
propargyl alcohol
temperature

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Rhodium-catalyzed transformation of propargyl alcohol derivatives to 2-silylmethyl-2-alkenals. / Matsuda, Isamu; Niikawa, Nakayoshi; Kuwabara, Rika; Inoue, Hirofumi; Nagashima, Hideo; Itoh, Kenji.

In: Journal of Organometallic Chemistry, Vol. 574, No. 1, 08.02.1999, p. 133-141.

Research output: Contribution to journalArticle

Matsuda, Isamu ; Niikawa, Nakayoshi ; Kuwabara, Rika ; Inoue, Hirofumi ; Nagashima, Hideo ; Itoh, Kenji. / Rhodium-catalyzed transformation of propargyl alcohol derivatives to 2-silylmethyl-2-alkenals. In: Journal of Organometallic Chemistry. 1999 ; Vol. 574, No. 1. pp. 133-141.
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AU - Nagashima, Hideo

AU - Itoh, Kenji

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