Intramolecular Reaction of (γ-Alkoxyallyl)stannane with Aldehyde: Origin of the Stereoselectivities

Isao Kadota, Miho Kawada, Vladimir Gevorgyan, Yoshinori Yamamoto

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36 Citations (Scopus)

Abstract

The intramolecular cyclization of simple acyclic (γ-alkoxyallyl)stannane aldehydes 1, 2, and 12-15 was investigated to elucidate the relationship between the geometry of the double bond of the allylstannanes, the ring size of cyclic ethers produced by the cyclization, and the procedures for promoting the cyclization. The Lewis acid-mediated cyclization of 1-2, 12-13, and 14-15 gave the trans cyclic ethers 3, 39, and 41, respectively, either predominantly or exclusively irrespective of the geometry of the double bond and of the ring size of the cyclic ethers. The relationship in the thermal cyclization of 1 and 2, which gave the 6-membered cyclic ethers 4 and 3, was straightforward; the Z isomer 1 gave the cis product 4, and the E isomer 2 afforded the trans product 3. However, the relationship in the thermal cyclization of 12 and 13 which afforded the 5-membered cyclic ethers 39 and 40 was different from that expected from the cyclization via the well-accepted cyclic transition state, as observed in the case of 1 and 2. Both the Z (12) and E (13) isomers gave the cis cyclic ether 40 either predominantly or exclusively. The protic acid-mediated (or -catalyzed) cyclization of 12-13 and 14-15 gave the trans cyclic ethers 39 and 41, respectively, regardless of the geometry of the double bonds. On the other hand, the protic acid-promoted cyclization of 1 and 2 was very strange; the Z isomer 1 gave the cis isomer 4, and the E isomer 2 afforded the trans isomer 3. The mechanisms for these cyclization reactions are proposed.

Original languageEnglish
Pages (from-to)7439-7446
Number of pages8
JournalJournal of Organic Chemistry
Volume62
Issue number21
Publication statusPublished - 1997
Externally publishedYes

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Stereoselectivity
Cyclization
Cyclic Ethers
Aldehydes
Isomers
Geometry
stannane
Lewis Acids
Acids

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Intramolecular Reaction of (γ-Alkoxyallyl)stannane with Aldehyde : Origin of the Stereoselectivities. / Kadota, Isao; Kawada, Miho; Gevorgyan, Vladimir; Yamamoto, Yoshinori.

In: Journal of Organic Chemistry, Vol. 62, No. 21, 1997, p. 7439-7446.

Research output: Contribution to journalArticle

Kadota, Isao ; Kawada, Miho ; Gevorgyan, Vladimir ; Yamamoto, Yoshinori. / Intramolecular Reaction of (γ-Alkoxyallyl)stannane with Aldehyde : Origin of the Stereoselectivities. In: Journal of Organic Chemistry. 1997 ; Vol. 62, No. 21. pp. 7439-7446.
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