Base-Induced Dehydrogenative and Dearomative Transformation of 1-Naphthylmethylamines to 1,4-Dihydronaphthalene-1-carbonitriles

Yoshiya Sekiguchi; Jia Hao Pang; Jia Sheng Ng; Jiahua Chen; Kohei Watanabe; Ryo Takita; Shunsuke Chiba

doi:10.1021/jacsau.2c00487

Base-Induced Dehydrogenative and Dearomative Transformation of 1-Naphthylmethylamines to 1,4-Dihydronaphthalene-1-carbonitriles

Yoshiya Sekiguchi, Jia Hao Pang, Jia Sheng Ng, Jiahua Chen, Kohei Watanabe, Ryo Takita^*, Shunsuke Chiba^*

^*Corresponding author for this work

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

3 Citations (Scopus)

Abstract

Solvothermal treatment of 1-naphthylmethylamine with potassium hydride (KH) or n-butyllithium (n-BuLi)-potassium t-butoxide (t-BuOK) in THF induces unusual two consecutive β-hydride eliminations to form 1-naphthonitrile and KH. The freshly generated KH is hydridic enough to undergo dearomative hydride addition to the resultant 1-naphthonitrile regioselectively at the C4 position to afford α-cyano benzylic carbanion, which could be functionalized by a series of electrophiles, liberating the corresponding 1,4-dihydronaphthalene-1-carbonitriles having a quaternary carbon center.

Original language	English
Pages (from-to)	2758-2764
Number of pages	7
Journal	JACS Au
Volume	2
Issue number	12
DOIs	https://doi.org/10.1021/jacsau.2c00487
Publication status	Published - Dec 26 2022
Externally published	Yes

Bibliographical note

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© 2022 American Chemical Society. All rights reserved.

ASJC Scopus Subject Areas

Analytical Chemistry
Chemistry (miscellaneous)
Physical and Theoretical Chemistry
Organic Chemistry

Keywords

dearomatization
DFT calculations
potassium amides
potassium hydride
β-hydride elimination

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10.1021/jacsau.2c00487

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title = "Base-Induced Dehydrogenative and Dearomative Transformation of 1-Naphthylmethylamines to 1,4-Dihydronaphthalene-1-carbonitriles",

abstract = "Solvothermal treatment of 1-naphthylmethylamine with potassium hydride (KH) or n-butyllithium (n-BuLi)-potassium t-butoxide (t-BuOK) in THF induces unusual two consecutive β-hydride eliminations to form 1-naphthonitrile and KH. The freshly generated KH is hydridic enough to undergo dearomative hydride addition to the resultant 1-naphthonitrile regioselectively at the C4 position to afford α-cyano benzylic carbanion, which could be functionalized by a series of electrophiles, liberating the corresponding 1,4-dihydronaphthalene-1-carbonitriles having a quaternary carbon center.",

keywords = "dearomatization, DFT calculations, potassium amides, potassium hydride, β-hydride elimination",

author = "Yoshiya Sekiguchi and Pang, {Jia Hao} and Ng, {Jia Sheng} and Jiahua Chen and Kohei Watanabe and Ryo Takita and Shunsuke Chiba",

year = "2022",

month = dec,

day = "26",

doi = "10.1021/jacsau.2c00487",

language = "English",

volume = "2",

pages = "2758--2764",

journal = "JACS Au",

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T1 - Base-Induced Dehydrogenative and Dearomative Transformation of 1-Naphthylmethylamines to 1,4-Dihydronaphthalene-1-carbonitriles

AU - Sekiguchi, Yoshiya

AU - Pang, Jia Hao

AU - Ng, Jia Sheng

AU - Chen, Jiahua

AU - Watanabe, Kohei

AU - Takita, Ryo

AU - Chiba, Shunsuke

PY - 2022/12/26

Y1 - 2022/12/26

N2 - Solvothermal treatment of 1-naphthylmethylamine with potassium hydride (KH) or n-butyllithium (n-BuLi)-potassium t-butoxide (t-BuOK) in THF induces unusual two consecutive β-hydride eliminations to form 1-naphthonitrile and KH. The freshly generated KH is hydridic enough to undergo dearomative hydride addition to the resultant 1-naphthonitrile regioselectively at the C4 position to afford α-cyano benzylic carbanion, which could be functionalized by a series of electrophiles, liberating the corresponding 1,4-dihydronaphthalene-1-carbonitriles having a quaternary carbon center.

AB - Solvothermal treatment of 1-naphthylmethylamine with potassium hydride (KH) or n-butyllithium (n-BuLi)-potassium t-butoxide (t-BuOK) in THF induces unusual two consecutive β-hydride eliminations to form 1-naphthonitrile and KH. The freshly generated KH is hydridic enough to undergo dearomative hydride addition to the resultant 1-naphthonitrile regioselectively at the C4 position to afford α-cyano benzylic carbanion, which could be functionalized by a series of electrophiles, liberating the corresponding 1,4-dihydronaphthalene-1-carbonitriles having a quaternary carbon center.

KW - dearomatization

KW - DFT calculations

KW - potassium amides

KW - potassium hydride

KW - β-hydride elimination

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U2 - 10.1021/jacsau.2c00487

DO - 10.1021/jacsau.2c00487

M3 - Article

AN - SCOPUS:85143488331

SN - 2691-3704

VL - 2

SP - 2758

EP - 2764

JO - JACS Au

JF - JACS Au

IS - 12

ER -

Base-Induced Dehydrogenative and Dearomative Transformation of 1-Naphthylmethylamines to 1,4-Dihydronaphthalene-1-carbonitriles

Abstract

Bibliographical note

ASJC Scopus Subject Areas

Keywords

Access to Document

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