Development of the First Spiro Bis(isoxazoline)Ligands (SPRIXs) and Their Applications to Catalytic Enantioselective Reactions

Midori A. Arai; Toshio Shinohara; Takayoshi Aral; Hiroaki Sasai

doi:10.5059/yukigoseikyokaishi.62.59

Development of the First Spiro Bis(isoxazoline)Ligands (SPRIXs) and Their Applications to Catalytic Enantioselective Reactions

Midori A. Arai, Toshio Shinohara, Takayoshi Aral, Hiroaki Sasai

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

4 Citations (Scopus)

Abstract

The first chiral isoxazoline ligands bearing spiro skeleton are developed. The spiro bis(isoxazoline) ligands (SPRIXs) are readily synthesized from diethyl malonate via double intramolecular nitrile oxide cycloaddition as a key step. The complex of (M, S, S)-R-SPRIX and Pd(OCOCF₃)₂ promoted the catalytic asymmetric Wacker-type cyclization of alkenyl alcohols to give optically active cyclic ethers for the first time. Furthermore, starting from dialkenyl alcohol, the enantioselective tandem cyclization via oxy-palladation was achieved with up to 95% ee. Asymmetric ligands other than SPRIKs promote neither the Wacker-type reaction nor the tandem reaction.

Original language	English
Pages (from-to)	59-69
Number of pages	11
Journal	Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry
Volume	62
Issue number	1
DOIs	https://doi.org/10.5059/yukigoseikyokaishi.62.59
Publication status	Published - 2004 Jan
Externally published	Yes

Keywords

Isoxazoline
Nitrile oxide cycloaddition
Palladium
Spiro
Tandem reaction
Wacker-reaction

ASJC Scopus subject areas

Organic Chemistry

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Development of the First Spiro Bis(isoxazoline)Ligands (SPRIXs) and Their Applications to Catalytic Enantioselective Reactions. / Arai, Midori A.; Shinohara, Toshio; Aral, Takayoshi; Sasai, Hiroaki.

In: Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry, Vol. 62, No. 1, 01.2004, p. 59-69.

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

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abstract = "The first chiral isoxazoline ligands bearing spiro skeleton are developed. The spiro bis(isoxazoline) ligands (SPRIXs) are readily synthesized from diethyl malonate via double intramolecular nitrile oxide cycloaddition as a key step. The complex of (M, S, S)-R-SPRIX and Pd(OCOCF3)2 promoted the catalytic asymmetric Wacker-type cyclization of alkenyl alcohols to give optically active cyclic ethers for the first time. Furthermore, starting from dialkenyl alcohol, the enantioselective tandem cyclization via oxy-palladation was achieved with up to 95% ee. Asymmetric ligands other than SPRIKs promote neither the Wacker-type reaction nor the tandem reaction.",

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AU - Arai, Midori A.

AU - Shinohara, Toshio

AU - Aral, Takayoshi

AU - Sasai, Hiroaki

PY - 2004/1

Y1 - 2004/1

N2 - The first chiral isoxazoline ligands bearing spiro skeleton are developed. The spiro bis(isoxazoline) ligands (SPRIXs) are readily synthesized from diethyl malonate via double intramolecular nitrile oxide cycloaddition as a key step. The complex of (M, S, S)-R-SPRIX and Pd(OCOCF3)2 promoted the catalytic asymmetric Wacker-type cyclization of alkenyl alcohols to give optically active cyclic ethers for the first time. Furthermore, starting from dialkenyl alcohol, the enantioselective tandem cyclization via oxy-palladation was achieved with up to 95% ee. Asymmetric ligands other than SPRIKs promote neither the Wacker-type reaction nor the tandem reaction.

AB - The first chiral isoxazoline ligands bearing spiro skeleton are developed. The spiro bis(isoxazoline) ligands (SPRIXs) are readily synthesized from diethyl malonate via double intramolecular nitrile oxide cycloaddition as a key step. The complex of (M, S, S)-R-SPRIX and Pd(OCOCF3)2 promoted the catalytic asymmetric Wacker-type cyclization of alkenyl alcohols to give optically active cyclic ethers for the first time. Furthermore, starting from dialkenyl alcohol, the enantioselective tandem cyclization via oxy-palladation was achieved with up to 95% ee. Asymmetric ligands other than SPRIKs promote neither the Wacker-type reaction nor the tandem reaction.

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KW - Nitrile oxide cycloaddition

KW - Palladium

KW - Spiro

KW - Tandem reaction

KW - Wacker-reaction

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Development of the First Spiro Bis(isoxazoline)Ligands (SPRIXs) and Their Applications to Catalytic Enantioselective Reactions

Abstract

Keywords

ASJC Scopus subject areas

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