Catalytic Enantioselective Synthesis of Azepine-Fused Planar-Chiral Ferrocenes by Pt-Catalyzed Cycloisomerization

Mamoru Ito; Moeka Okamura; Kyalo Stephen Kanyiva; Takanori Shibata

doi:10.1021/acs.organomet.9b00422

Catalytic Enantioselective Synthesis of Azepine-Fused Planar-Chiral Ferrocenes by Pt-Catalyzed Cycloisomerization

Mamoru Ito^*, Moeka Okamura, Kyalo Stephen Kanyiva, Takanori Shibata

^*Corresponding author for this work

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

14 Citations (Scopus)

Abstract

Enantioselective synthesis of azepine-fused planar-chiral ferrocenes was achieved by the chiral cationic Pt-catalyzed intramolecular cycloisomerization of N-propargyl-2-ferrocenylanilines. A mechanistic study using an N-allenyl analogue indicated that the reaction proceeded selectively in a 7-exo-dig manner along with isomerization of the exo-olefin moiety. A methanesulfonylamino tether was crucial for selective cycloisomerization. This is the first example of the enantioselective synthesis of heteropin-fused planar-chiral ferrocenes.

Original language	English
Pages (from-to)	4029-4035
Number of pages	7
Journal	Organometallics
Volume	38
Issue number	20
DOIs	https://doi.org/10.1021/acs.organomet.9b00422
Publication status	Published - 2019 Oct 28

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/acs.organomet.9b00422

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title = "Catalytic Enantioselective Synthesis of Azepine-Fused Planar-Chiral Ferrocenes by Pt-Catalyzed Cycloisomerization",

abstract = "Enantioselective synthesis of azepine-fused planar-chiral ferrocenes was achieved by the chiral cationic Pt-catalyzed intramolecular cycloisomerization of N-propargyl-2-ferrocenylanilines. A mechanistic study using an N-allenyl analogue indicated that the reaction proceeded selectively in a 7-exo-dig manner along with isomerization of the exo-olefin moiety. A methanesulfonylamino tether was crucial for selective cycloisomerization. This is the first example of the enantioselective synthesis of heteropin-fused planar-chiral ferrocenes.",

author = "Mamoru Ito and Moeka Okamura and Kanyiva, {Kyalo Stephen} and Takanori Shibata",

note = "Funding Information: This work was supported by a Mitsubishi Material Corporation and Waseda University Joint Cooperation Grant. We thank Ms. Ninna Uno (Waseda University) for some initial experiments. Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

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doi = "10.1021/acs.organomet.9b00422",

language = "English",

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T1 - Catalytic Enantioselective Synthesis of Azepine-Fused Planar-Chiral Ferrocenes by Pt-Catalyzed Cycloisomerization

AU - Ito, Mamoru

AU - Okamura, Moeka

AU - Kanyiva, Kyalo Stephen

AU - Shibata, Takanori

N1 - Funding Information: This work was supported by a Mitsubishi Material Corporation and Waseda University Joint Cooperation Grant. We thank Ms. Ninna Uno (Waseda University) for some initial experiments. Publisher Copyright: © 2019 American Chemical Society.

PY - 2019/10/28

Y1 - 2019/10/28

N2 - Enantioselective synthesis of azepine-fused planar-chiral ferrocenes was achieved by the chiral cationic Pt-catalyzed intramolecular cycloisomerization of N-propargyl-2-ferrocenylanilines. A mechanistic study using an N-allenyl analogue indicated that the reaction proceeded selectively in a 7-exo-dig manner along with isomerization of the exo-olefin moiety. A methanesulfonylamino tether was crucial for selective cycloisomerization. This is the first example of the enantioselective synthesis of heteropin-fused planar-chiral ferrocenes.

AB - Enantioselective synthesis of azepine-fused planar-chiral ferrocenes was achieved by the chiral cationic Pt-catalyzed intramolecular cycloisomerization of N-propargyl-2-ferrocenylanilines. A mechanistic study using an N-allenyl analogue indicated that the reaction proceeded selectively in a 7-exo-dig manner along with isomerization of the exo-olefin moiety. A methanesulfonylamino tether was crucial for selective cycloisomerization. This is the first example of the enantioselective synthesis of heteropin-fused planar-chiral ferrocenes.

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SN - 0276-7333

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Catalytic Enantioselective Synthesis of Azepine-Fused Planar-Chiral Ferrocenes by Pt-Catalyzed Cycloisomerization

Abstract

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