Pentamethylcyclopentadienide in organic synthesis: Nucleophilic addition of lithium pentamethylcyclopentadienide to carbonyl compounds and carbon-carbon bond cleavage of the adducts yielding the parent carbonyl compounds

Minoru Uemura; Kazunari Yagi; Masayuki Iwasaki; Kenichi Nomura; Hideki Yorimitsu; Koichiro Oshima

doi:10.1016/j.tet.2006.01.097

Pentamethylcyclopentadienide in organic synthesis: Nucleophilic addition of lithium pentamethylcyclopentadienide to carbonyl compounds and carbon-carbon bond cleavage of the adducts yielding the parent carbonyl compounds

Minoru Uemura, Kazunari Yagi, Masayuki Iwasaki, Kenichi Nomura, Hideki Yorimitsu, Koichiro Oshima

Research output: Contribution to journal › Article › peer-review

10 Citations (Scopus)

Abstract

Lithium pentamethylcyclopentadienide (C₅Me₅Li, Cp*Li) reacted with aromatic aldehyde to provide the corresponding carbinol in excellent yield. The carbinol returns to the parent aldehyde and pentamethylcyclopentadiene upon exposure to acid or due to heating. Chlorodimethylaluminum is essential as an additive to attain the nucleophilic addition of Cp*Li to aliphatic aldehyde. The carbinol derived from aliphatic aldehyde returns to the parent aldehyde and pentamethylcyclopentadiene by the action of a catalytic amount of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). The reversible addition/elimination of the Cp* group can represent a protection of aldehyde. Mechanistic details of the carbon-carbon bond cleavage are also disclosed.

Original language	English
Pages (from-to)	3523-3535
Number of pages	13
Journal	Tetrahedron
Volume	62
Issue number	15
DOIs	https://doi.org/10.1016/j.tet.2006.01.097
Publication status	Published - Apr 10 2006
Externally published	Yes

Keywords

Carbon-carbon bond cleavage
Carbonyl compounds
Nucleophilic addition
Pentamethylcyclopentadiene
Protection

ASJC Scopus subject areas

Biochemistry
Drug Discovery
Organic Chemistry

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Uemura, M., Yagi, K., Iwasaki, M., Nomura, K., Yorimitsu, H., & Oshima, K. (2006). Pentamethylcyclopentadienide in organic synthesis: Nucleophilic addition of lithium pentamethylcyclopentadienide to carbonyl compounds and carbon-carbon bond cleavage of the adducts yielding the parent carbonyl compounds. Tetrahedron, 62(15), 3523-3535. https://doi.org/10.1016/j.tet.2006.01.097

Pentamethylcyclopentadienide in organic synthesis : Nucleophilic addition of lithium pentamethylcyclopentadienide to carbonyl compounds and carbon-carbon bond cleavage of the adducts yielding the parent carbonyl compounds. / Uemura, Minoru; Yagi, Kazunari; Iwasaki, Masayuki et al.

In: Tetrahedron, Vol. 62, No. 15, 10.04.2006, p. 3523-3535.

Research output: Contribution to journal › Article › peer-review

Uemura, M, Yagi, K, Iwasaki, M, Nomura, K, Yorimitsu, H & Oshima, K 2006, 'Pentamethylcyclopentadienide in organic synthesis: Nucleophilic addition of lithium pentamethylcyclopentadienide to carbonyl compounds and carbon-carbon bond cleavage of the adducts yielding the parent carbonyl compounds', Tetrahedron, vol. 62, no. 15, pp. 3523-3535. https://doi.org/10.1016/j.tet.2006.01.097

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abstract = "Lithium pentamethylcyclopentadienide (C5Me5Li, Cp*Li) reacted with aromatic aldehyde to provide the corresponding carbinol in excellent yield. The carbinol returns to the parent aldehyde and pentamethylcyclopentadiene upon exposure to acid or due to heating. Chlorodimethylaluminum is essential as an additive to attain the nucleophilic addition of Cp*Li to aliphatic aldehyde. The carbinol derived from aliphatic aldehyde returns to the parent aldehyde and pentamethylcyclopentadiene by the action of a catalytic amount of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). The reversible addition/elimination of the Cp* group can represent a protection of aldehyde. Mechanistic details of the carbon-carbon bond cleavage are also disclosed.",

keywords = "Carbon-carbon bond cleavage, Carbonyl compounds, Nucleophilic addition, Pentamethylcyclopentadiene, Protection",

author = "Minoru Uemura and Kazunari Yagi and Masayuki Iwasaki and Kenichi Nomura and Hideki Yorimitsu and Koichiro Oshima",

note = "Funding Information: This work is supported by Grants-in-Aid for Scientific Research, Young Scientists, and COE Research from the Ministry of Education, Culture, Sports, Science, and Technology, Japan. ",

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AU - Yagi, Kazunari

AU - Iwasaki, Masayuki

AU - Nomura, Kenichi

AU - Yorimitsu, Hideki

AU - Oshima, Koichiro

N1 - Funding Information: This work is supported by Grants-in-Aid for Scientific Research, Young Scientists, and COE Research from the Ministry of Education, Culture, Sports, Science, and Technology, Japan.

PY - 2006/4/10

Y1 - 2006/4/10

N2 - Lithium pentamethylcyclopentadienide (C5Me5Li, Cp*Li) reacted with aromatic aldehyde to provide the corresponding carbinol in excellent yield. The carbinol returns to the parent aldehyde and pentamethylcyclopentadiene upon exposure to acid or due to heating. Chlorodimethylaluminum is essential as an additive to attain the nucleophilic addition of Cp*Li to aliphatic aldehyde. The carbinol derived from aliphatic aldehyde returns to the parent aldehyde and pentamethylcyclopentadiene by the action of a catalytic amount of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). The reversible addition/elimination of the Cp* group can represent a protection of aldehyde. Mechanistic details of the carbon-carbon bond cleavage are also disclosed.

AB - Lithium pentamethylcyclopentadienide (C5Me5Li, Cp*Li) reacted with aromatic aldehyde to provide the corresponding carbinol in excellent yield. The carbinol returns to the parent aldehyde and pentamethylcyclopentadiene upon exposure to acid or due to heating. Chlorodimethylaluminum is essential as an additive to attain the nucleophilic addition of Cp*Li to aliphatic aldehyde. The carbinol derived from aliphatic aldehyde returns to the parent aldehyde and pentamethylcyclopentadiene by the action of a catalytic amount of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). The reversible addition/elimination of the Cp* group can represent a protection of aldehyde. Mechanistic details of the carbon-carbon bond cleavage are also disclosed.

KW - Carbon-carbon bond cleavage

KW - Carbonyl compounds

KW - Nucleophilic addition

KW - Pentamethylcyclopentadiene

KW - Protection

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Pentamethylcyclopentadienide in organic synthesis: Nucleophilic addition of lithium pentamethylcyclopentadienide to carbonyl compounds and carbon-carbon bond cleavage of the adducts yielding the parent carbonyl compounds

Abstract

Keywords

ASJC Scopus subject areas

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