Convergent Azaspirocyclization of Bromoarenes with N-Tosylhydrazones by a Palladium Catalyst

Aika Yanagimoto; Yota Uwabe; Qikun Wu; Kei Muto; Junichiro Yamaguchi

doi:10.1021/acscatal.1c02627

Convergent Azaspirocyclization of Bromoarenes with N-Tosylhydrazones by a Palladium Catalyst

Aika Yanagimoto, Yota Uwabe, Qikun Wu, Kei Muto^*, Junichiro Yamaguchi^*

^*Corresponding author for this work

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

9 Citations (Scopus)

Abstract

1-Azaspirocyclic compounds have gained attention in chemistry and drug discovery fields. In this manuscript, the development of a Pd-catalyzed dearomative azaspirocyclization of bromoarenes bearing an aminoalkyl group with N-tosylhydrazones is described. The present method enables azaspirocyclization with the introduction of carbon substituents, achieving the convergent synthesis of 1-azaspirocycles. This method allowed furan, thiophene, and naphthalene cores to generate the corresponding 1-azaspirocycles. The obtained azaspirocycles from furans were further elaborated via an acid-catalyzed rearrangement to afford 1-azaspirocyclopentenones.

Original language	English
Pages (from-to)	10429-10435
Number of pages	7
Journal	ACS Catalysis
Volume	11
DOIs	https://doi.org/10.1021/acscatal.1c02627
Publication status	Published - 2021

Keywords

Pd-carbene
bromoarenes
dearomatization
palladium
spirocyclic compounds

ASJC Scopus subject areas

Catalysis
Chemistry(all)

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10.1021/acscatal.1c02627

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@article{f28af770e9c04d62ab666d78ef9fc308,

title = "Convergent Azaspirocyclization of Bromoarenes with N-Tosylhydrazones by a Palladium Catalyst",

abstract = "1-Azaspirocyclic compounds have gained attention in chemistry and drug discovery fields. In this manuscript, the development of a Pd-catalyzed dearomative azaspirocyclization of bromoarenes bearing an aminoalkyl group with N-tosylhydrazones is described. The present method enables azaspirocyclization with the introduction of carbon substituents, achieving the convergent synthesis of 1-azaspirocycles. This method allowed furan, thiophene, and naphthalene cores to generate the corresponding 1-azaspirocycles. The obtained azaspirocycles from furans were further elaborated via an acid-catalyzed rearrangement to afford 1-azaspirocyclopentenones. ",

keywords = "Pd-carbene, bromoarenes, dearomatization, palladium, spirocyclic compounds",

author = "Aika Yanagimoto and Yota Uwabe and Qikun Wu and Kei Muto and Junichiro Yamaguchi",

note = "Funding Information: This work was supported by JSPS KAKENHI Grant Number JP19H02726 (to J.Y.), JP20H04829 (hybrid catalysis), JP21K05079, and Sumitomo Foundation (to K.M.). This work was also partly supported by JST ERATO Grant Number JPMJER1901 (to J.Y.). We thank Dr. Kenta Kato (Waseda University) for assistance with X-ray crystallographic analysis. We thank Iwatani Corporation for providing CsCO as a gift. The Materials Characterization Central Laboratory in Waseda University is acknowledged for the support of HRMS measurement. 2 3 Publisher Copyright: {\textcopyright} ",

year = "2021",

doi = "10.1021/acscatal.1c02627",

language = "English",

volume = "11",

pages = "10429--10435",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

}

TY - JOUR

T1 - Convergent Azaspirocyclization of Bromoarenes with N-Tosylhydrazones by a Palladium Catalyst

AU - Yanagimoto, Aika

AU - Uwabe, Yota

AU - Wu, Qikun

AU - Muto, Kei

AU - Yamaguchi, Junichiro

N1 - Funding Information: This work was supported by JSPS KAKENHI Grant Number JP19H02726 (to J.Y.), JP20H04829 (hybrid catalysis), JP21K05079, and Sumitomo Foundation (to K.M.). This work was also partly supported by JST ERATO Grant Number JPMJER1901 (to J.Y.). We thank Dr. Kenta Kato (Waseda University) for assistance with X-ray crystallographic analysis. We thank Iwatani Corporation for providing CsCO as a gift. The Materials Characterization Central Laboratory in Waseda University is acknowledged for the support of HRMS measurement. 2 3 Publisher Copyright: ©

PY - 2021

Y1 - 2021

N2 - 1-Azaspirocyclic compounds have gained attention in chemistry and drug discovery fields. In this manuscript, the development of a Pd-catalyzed dearomative azaspirocyclization of bromoarenes bearing an aminoalkyl group with N-tosylhydrazones is described. The present method enables azaspirocyclization with the introduction of carbon substituents, achieving the convergent synthesis of 1-azaspirocycles. This method allowed furan, thiophene, and naphthalene cores to generate the corresponding 1-azaspirocycles. The obtained azaspirocycles from furans were further elaborated via an acid-catalyzed rearrangement to afford 1-azaspirocyclopentenones.

AB - 1-Azaspirocyclic compounds have gained attention in chemistry and drug discovery fields. In this manuscript, the development of a Pd-catalyzed dearomative azaspirocyclization of bromoarenes bearing an aminoalkyl group with N-tosylhydrazones is described. The present method enables azaspirocyclization with the introduction of carbon substituents, achieving the convergent synthesis of 1-azaspirocycles. This method allowed furan, thiophene, and naphthalene cores to generate the corresponding 1-azaspirocycles. The obtained azaspirocycles from furans were further elaborated via an acid-catalyzed rearrangement to afford 1-azaspirocyclopentenones.

KW - Pd-carbene

KW - bromoarenes

KW - dearomatization

KW - palladium

KW - spirocyclic compounds

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U2 - 10.1021/acscatal.1c02627

DO - 10.1021/acscatal.1c02627

M3 - Article

AN - SCOPUS:85113788262

SN - 2155-5435

VL - 11

SP - 10429

EP - 10435

JO - ACS Catalysis

JF - ACS Catalysis

ER -

Convergent Azaspirocyclization of Bromoarenes with N-Tosylhydrazones by a Palladium Catalyst

Abstract

Keywords

ASJC Scopus subject areas

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