Organophosphane-Catalyzed Construction of Functionalized 2-Ylideneoxindoles via Direct β-Acylation

Wey Chyng Jeng; Po Chung Chien; Sandip Sambhaji Vagh; Athukuri Edukondalu; Wenwei Lin

doi:10.1055/a-1549-1082

Organophosphane-Catalyzed Construction of Functionalized 2-Ylideneoxindoles via Direct β-Acylation

Wey Chyng Jeng, Po Chung Chien, Sandip Sambhaji Vagh, Athukuri Edukondalu, Wenwei Lin^*

^*Corresponding author for this work

Department of Chemistry

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

1 Citation (Scopus)

Abstract

We report an efficient method for the direct β-acylation of 2-ylideneoxindoles with acyl chlorides that is catalyzed by organophosphanes in the presence of base. A variety of functionalized 2-ylideneoxindoles were prepared in moderate to good yields under mild, metalfree conditions via a tandem phospha-Michael/O-acylation/intramolecular cyclization/rearrangement sequence. Mechanistic investigations revealed that C-O bond cleavage on a possible betaine intermediate is the key step for the installation of the keto-functionality at the β-position of 2-ylideneoxindoles in a highly stereospecific manner. The synthetic utility of this protocol could also be proven by a scale-up reaction and synthetic transformations of the products.

Original language	English
Pages (from-to)	4409-4418
Number of pages	10
Journal	Synthesis (Germany)
Volume	53
Issue number	23
DOIs	https://doi.org/10.1055/a-1549-1082
Publication status	Published - 2021 Aug 16

Keywords

functionalized 2-ylideneoxindoles
indolin-3-ones
phospha-Michael addition
phosphine catalysis
β-acylation

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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10.1055/a-1549-1082

Cite this

@article{8456bca5c27640aaab42403066a151a2,

title = "Organophosphane-Catalyzed Construction of Functionalized 2-Ylideneoxindoles via Direct β-Acylation",

abstract = "We report an efficient method for the direct β-acylation of 2-ylideneoxindoles with acyl chlorides that is catalyzed by organophosphanes in the presence of base. A variety of functionalized 2-ylideneoxindoles were prepared in moderate to good yields under mild, metalfree conditions via a tandem phospha-Michael/O-acylation/intramolecular cyclization/rearrangement sequence. Mechanistic investigations revealed that C-O bond cleavage on a possible betaine intermediate is the key step for the installation of the keto-functionality at the β-position of 2-ylideneoxindoles in a highly stereospecific manner. The synthetic utility of this protocol could also be proven by a scale-up reaction and synthetic transformations of the products.",

keywords = "functionalized 2-ylideneoxindoles, indolin-3-ones, phospha-Michael addition, phosphine catalysis, β-acylation",

author = "Jeng, {Wey Chyng} and Chien, {Po Chung} and Vagh, {Sandip Sambhaji} and Athukuri Edukondalu and Wenwei Lin",

year = "2021",

month = aug,

day = "16",

doi = "10.1055/a-1549-1082",

language = "English",

volume = "53",

pages = "4409--4418",

journal = "Synthesis (Germany)",

issn = "0039-7881",

publisher = "Georg Thieme Verlag",

number = "23",

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TY - JOUR

T1 - Organophosphane-Catalyzed Construction of Functionalized 2-Ylideneoxindoles via Direct β-Acylation

AU - Jeng, Wey Chyng

AU - Chien, Po Chung

AU - Vagh, Sandip Sambhaji

AU - Edukondalu, Athukuri

AU - Lin, Wenwei

PY - 2021/8/16

Y1 - 2021/8/16

N2 - We report an efficient method for the direct β-acylation of 2-ylideneoxindoles with acyl chlorides that is catalyzed by organophosphanes in the presence of base. A variety of functionalized 2-ylideneoxindoles were prepared in moderate to good yields under mild, metalfree conditions via a tandem phospha-Michael/O-acylation/intramolecular cyclization/rearrangement sequence. Mechanistic investigations revealed that C-O bond cleavage on a possible betaine intermediate is the key step for the installation of the keto-functionality at the β-position of 2-ylideneoxindoles in a highly stereospecific manner. The synthetic utility of this protocol could also be proven by a scale-up reaction and synthetic transformations of the products.

AB - We report an efficient method for the direct β-acylation of 2-ylideneoxindoles with acyl chlorides that is catalyzed by organophosphanes in the presence of base. A variety of functionalized 2-ylideneoxindoles were prepared in moderate to good yields under mild, metalfree conditions via a tandem phospha-Michael/O-acylation/intramolecular cyclization/rearrangement sequence. Mechanistic investigations revealed that C-O bond cleavage on a possible betaine intermediate is the key step for the installation of the keto-functionality at the β-position of 2-ylideneoxindoles in a highly stereospecific manner. The synthetic utility of this protocol could also be proven by a scale-up reaction and synthetic transformations of the products.

KW - functionalized 2-ylideneoxindoles

KW - indolin-3-ones

KW - phospha-Michael addition

KW - phosphine catalysis

KW - β-acylation

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U2 - 10.1055/a-1549-1082

DO - 10.1055/a-1549-1082

M3 - Article

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SN - 0039-7881

VL - 53

SP - 4409

EP - 4418

JO - Synthesis (Germany)

JF - Synthesis (Germany)

IS - 23

ER -

Organophosphane-Catalyzed Construction of Functionalized 2-Ylideneoxindoles via Direct β-Acylation

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

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CCDC 2086884: Experimental Crystal Structure Determination

CCDC 2089146: Experimental Crystal Structure Determination

Cite this

Organophosphane-Catalyzed Construction of Functionalized 2-Ylideneoxindoles via Direct β-Acylation

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 2086884: Experimental Crystal Structure Determination

CCDC 2089146: Experimental Crystal Structure Determination

Cite this