Dielectrophilic Allenic Ketone-Enabled [4 + 2] Annulation with 3,3'-Bisoxindoles: Enantioselective Creation of Two Contiguous Quaternary Stereogenic Centers

Xiaodong Tang; Chuan Xiang Alvin Tan; Wai Lun Chan; Fuhao Zhang; Wenrui Zheng; Yixin Lu

doi:10.1021/acscatal.0c05225

Dielectrophilic Allenic Ketone-Enabled [4 + 2] Annulation with 3,3'-Bisoxindoles: Enantioselective Creation of Two Contiguous Quaternary Stereogenic Centers

Xiaodong Tang
, Chuan Xiang Alvin Tan
, Wai Lun Chan
, Fuhao Zhang
, Wenrui Zheng
, Yixin Lu

Research output: Journal article publication › Journal article › Academic research › peer-review

41 Citations (Scopus)

Abstract

We introduced a type of allenic ketone as a dielectrophilic C4 synthon in phosphine-mediated reactions. The high electrophilicity of the advanced intermediates created upon phosphine activation empowered the utilization of 3,3′-bis-oxindoles as a two-carbon reaction partner in a highly enantioselective [4 + 2] annulation, allowing for facile creation of spirocyclic bisindoline structures containing two contiguous quaternary stereogenic centers. Synthetic manipulations of the [4 + 2] annulation product led to concise total synthesis of (-)-folicanthine.

Original language	English
Pages (from-to)	1361-1367
Number of pages	7
Journal	ACS Catalysis
Volume	11
Issue number	3
DOIs	https://doi.org/10.1021/acscatal.0c05225
Publication status	Published - 5 Feb 2021
Externally published	Yes

Keywords

allenic ketone
bifunctional phosphine
dielectrophilic
dinucleophilic
quaternary stereogenic centers
[4 + 2] annulation

ASJC Scopus subject areas

Catalysis
General Chemistry

More information

10.1021/acscatal.0c05225

Cite this

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title = "Dielectrophilic Allenic Ketone-Enabled [4 + 2] Annulation with 3,3'-Bisoxindoles: Enantioselective Creation of Two Contiguous Quaternary Stereogenic Centers",

abstract = "We introduced a type of allenic ketone as a dielectrophilic C4 synthon in phosphine-mediated reactions. The high electrophilicity of the advanced intermediates created upon phosphine activation empowered the utilization of 3,3′-bis-oxindoles as a two-carbon reaction partner in a highly enantioselective [4 + 2] annulation, allowing for facile creation of spirocyclic bisindoline structures containing two contiguous quaternary stereogenic centers. Synthetic manipulations of the [4 + 2] annulation product led to concise total synthesis of (-)-folicanthine.",

keywords = "allenic ketone, bifunctional phosphine, dielectrophilic, dinucleophilic, quaternary stereogenic centers, [4 + 2] annulation",

author = "Xiaodong Tang and Tan, \{Chuan Xiang Alvin\} and Chan, \{Wai Lun\} and Fuhao Zhang and Wenrui Zheng and Yixin Lu",

note = "Funding Information: Y.L. thanks the National Natural Science Foundation of China (21672158), the Singapore National Research Foundation (NRF) for the NRF Investigatorship Award (R-143-000-A15-281), and the National University of Singapore (R-143-000-695-114 and C-141-000-092-001) for generous financial support. Publisher Copyright: {\textcopyright}",

year = "2021",

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day = "5",

doi = "10.1021/acscatal.0c05225",

language = "English",

volume = "11",

pages = "1361--1367",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

number = "3",

}

Dielectrophilic Allenic Ketone-Enabled [4 + 2] Annulation with 3,3'-Bisoxindoles: Enantioselective Creation of Two Contiguous Quaternary Stereogenic Centers. / Tang, Xiaodong; Tan, Chuan Xiang Alvin; Chan, Wai Lun et al.
In: ACS Catalysis, Vol. 11, No. 3, 05.02.2021, p. 1361-1367.

Research output: Journal article publication › Journal article › Academic research › peer-review

TY - JOUR

T1 - Dielectrophilic Allenic Ketone-Enabled [4 + 2] Annulation with 3,3'-Bisoxindoles: Enantioselective Creation of Two Contiguous Quaternary Stereogenic Centers

AU - Tang, Xiaodong

AU - Tan, Chuan Xiang Alvin

AU - Chan, Wai Lun

AU - Zhang, Fuhao

AU - Zheng, Wenrui

AU - Lu, Yixin

N1 - Funding Information: Y.L. thanks the National Natural Science Foundation of China (21672158), the Singapore National Research Foundation (NRF) for the NRF Investigatorship Award (R-143-000-A15-281), and the National University of Singapore (R-143-000-695-114 and C-141-000-092-001) for generous financial support. Publisher Copyright: ©

PY - 2021/2/5

Y1 - 2021/2/5

N2 - We introduced a type of allenic ketone as a dielectrophilic C4 synthon in phosphine-mediated reactions. The high electrophilicity of the advanced intermediates created upon phosphine activation empowered the utilization of 3,3′-bis-oxindoles as a two-carbon reaction partner in a highly enantioselective [4 + 2] annulation, allowing for facile creation of spirocyclic bisindoline structures containing two contiguous quaternary stereogenic centers. Synthetic manipulations of the [4 + 2] annulation product led to concise total synthesis of (-)-folicanthine.

AB - We introduced a type of allenic ketone as a dielectrophilic C4 synthon in phosphine-mediated reactions. The high electrophilicity of the advanced intermediates created upon phosphine activation empowered the utilization of 3,3′-bis-oxindoles as a two-carbon reaction partner in a highly enantioselective [4 + 2] annulation, allowing for facile creation of spirocyclic bisindoline structures containing two contiguous quaternary stereogenic centers. Synthetic manipulations of the [4 + 2] annulation product led to concise total synthesis of (-)-folicanthine.

KW - allenic ketone

KW - bifunctional phosphine

KW - dielectrophilic

KW - dinucleophilic

KW - quaternary stereogenic centers

KW - [4 + 2] annulation

UR - https://www.scopus.com/pages/publications/85099988720

U2 - 10.1021/acscatal.0c05225

DO - 10.1021/acscatal.0c05225

M3 - Journal article

AN - SCOPUS:85099988720

SN - 2155-5435

VL - 11

SP - 1361

EP - 1367

JO - ACS Catalysis

JF - ACS Catalysis

IS - 3

ER -

Dielectrophilic Allenic Ketone-Enabled [4 + 2] Annulation with 3,3'-Bisoxindoles: Enantioselective Creation of Two Contiguous Quaternary Stereogenic Centers

Abstract

Keywords

ASJC Scopus subject areas

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