Synthesis of 3-Amino-1-benzothiophene-1,1-diones by Alkyne Directed Hydroarylation and 1/N→3/C-Sulfonyl Migration.

Ivan Bernar; Daniel Blanco-Ania; Sophie J. Stok; Lia Sotorríos; Enrique Gómez-Bengoa; Floris P. J. T. Rutjes

doi:10.1002/ejoc.201801062

Synthesis of 3-Amino-1-benzothiophene-1,1-diones by Alkyne Directed Hydroarylation and 1/N→3/C-Sulfonyl Migration.

Ivan Bernar, Daniel Blanco-Ania, Sophie J. Stok, Lia Sotorríos, Enrique Gómez-Bengoa, Floris P. J. T. Rutjes

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Abstract

A completely regioselective and highly stereoselective palladium-catalyzed intramolecular hydroarylation of arenesulfonyl ynamines to benzothiazoles was developed. The presence of an electron-withdrawing group on the triple bond of the sulfonyl ynamine was crucial for the success of the reaction and our mechanistic studies suggest an alkyne-directed 5-exo-dig cyclization pathway. The products easily underwent photoinduced rearrangement to 3-amino-1-benzothiophene-1,1-diones (up to 35 % yields after two steps).

Original language	English
Pages (from-to)	5435-5444
Number of pages	10
Journal	European Journal of Organic Chemistry
Volume	2018
Issue number	39
Early online date	14 Sept 2018
DOIs	https://doi.org/10.1002/ejoc.201801062
Publication status	Published - 24 Oct 2018

Keywords

Ynamines
homogeneous catalysis
palladium
C–H activation
synthetic methods

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10.1002/ejoc.201801062

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title = "Synthesis of 3-Amino-1-benzothiophene-1,1-diones by Alkyne Directed Hydroarylation and 1/N→3/C-Sulfonyl Migration.",

abstract = "A completely regioselective and highly stereoselective palladium-catalyzed intramolecular hydroarylation of arenesulfonyl ynamines to benzothiazoles was developed. The presence of an electron-withdrawing group on the triple bond of the sulfonyl ynamine was crucial for the success of the reaction and our mechanistic studies suggest an alkyne-directed 5-exo-dig cyclization pathway. The products easily underwent photoinduced rearrangement to 3-amino-1-benzothiophene-1,1-diones (up to 35 % yields after two steps).",

keywords = "Ynamines, homogeneous catalysis, palladium, C–H activation, synthetic methods",

author = "Ivan Bernar and Daniel Blanco-Ania and Stok, {Sophie J.} and Lia Sotorr{\'i}os and Enrique G{\'o}mez-Bengoa and Rutjes, {Floris P. J. T.}",

year = "2018",

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TY - JOUR

T1 - Synthesis of 3-Amino-1-benzothiophene-1,1-diones by Alkyne Directed Hydroarylation and 1/N→3/C-Sulfonyl Migration.

AU - Bernar, Ivan

AU - Blanco-Ania, Daniel

AU - Stok, Sophie J.

AU - Sotorríos, Lia

AU - Gómez-Bengoa, Enrique

AU - Rutjes, Floris P. J. T.

PY - 2018/10/24

Y1 - 2018/10/24

N2 - A completely regioselective and highly stereoselective palladium-catalyzed intramolecular hydroarylation of arenesulfonyl ynamines to benzothiazoles was developed. The presence of an electron-withdrawing group on the triple bond of the sulfonyl ynamine was crucial for the success of the reaction and our mechanistic studies suggest an alkyne-directed 5-exo-dig cyclization pathway. The products easily underwent photoinduced rearrangement to 3-amino-1-benzothiophene-1,1-diones (up to 35 % yields after two steps).

AB - A completely regioselective and highly stereoselective palladium-catalyzed intramolecular hydroarylation of arenesulfonyl ynamines to benzothiazoles was developed. The presence of an electron-withdrawing group on the triple bond of the sulfonyl ynamine was crucial for the success of the reaction and our mechanistic studies suggest an alkyne-directed 5-exo-dig cyclization pathway. The products easily underwent photoinduced rearrangement to 3-amino-1-benzothiophene-1,1-diones (up to 35 % yields after two steps).

KW - Ynamines

KW - homogeneous catalysis

KW - palladium

KW - C–H activation

KW - synthetic methods

UR - http://europepmc.org/abstract/med/30443160

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DO - 10.1002/ejoc.201801062

M3 - Article

C2 - 30443160

SN - 1434-193X

VL - 2018

SP - 5435

EP - 5444

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

IS - 39

ER -

Synthesis of 3-Amino-1-benzothiophene-1,1-diones by Alkyne Directed Hydroarylation and 1/N→3/C-Sulfonyl Migration.

Abstract

Keywords

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