Palladium-Titanium Relay Catalysis Enables Switch from Alkoxide-π-Allyl to Dienolate Reactivity for Spiro-Heterocycle Synthesis

Li Cheng Yang; Zher Yin Tan; Zi Qiang Rong; Ruoyang Liu; Ya Nong Wang; Yu Zhao

doi:10.1002/anie.201804160

Palladium-Titanium Relay Catalysis Enables Switch from Alkoxide-π-Allyl to Dienolate Reactivity for Spiro-Heterocycle Synthesis

Li Cheng Yang
, Zher Yin Tan
, Zi Qiang Rong
, Ruoyang Liu
, Ya Nong Wang
, Yu Zhao (Lead / Corresponding author)

Biological Chemistry and Drug Discovery

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

116 Citations (Scopus)

Abstract

Reported herein is the divergent syntheses of [5,5] and [6,5] spiro-heterocycles under Lewis-acid-assisted palladium catalysis. In particular, an unprecedented switch from alkoxide-π-allyl to dienolate reactivity was achieved by the use of palladium-titanium relay catalysis, and represents umpolung reactivity of vinylethylene carbonates. This method uses a simple procedure and commercially available catalysts, and delivers both classes of spiro-heterocycles, bearing three contiguous stereocenters, in high yield and uniformly excellent diastereoselectivity.

Original language	English
Pages (from-to)	7860-7864
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	57
Issue number	26
Early online date	9 May 2018
DOIs	https://doi.org/10.1002/anie.201804160
Publication status	Published - 25 Jun 2018

Keywords

cycloaddition
palladium
relay catalysis
spiro compounds
umpolung

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.201804160

Cite this

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title = "Palladium-Titanium Relay Catalysis Enables Switch from Alkoxide-π-Allyl to Dienolate Reactivity for Spiro-Heterocycle Synthesis",

abstract = "Reported herein is the divergent syntheses of [5,5] and [6,5] spiro-heterocycles under Lewis-acid-assisted palladium catalysis. In particular, an unprecedented switch from alkoxide-π-allyl to dienolate reactivity was achieved by the use of palladium-titanium relay catalysis, and represents umpolung reactivity of vinylethylene carbonates. This method uses a simple procedure and commercially available catalysts, and delivers both classes of spiro-heterocycles, bearing three contiguous stereocenters, in high yield and uniformly excellent diastereoselectivity.",

keywords = "cycloaddition, palladium, relay catalysis, spiro compounds, umpolung",

author = "Yang, \{Li Cheng\} and Tan, \{Zher Yin\} and Rong, \{Zi Qiang\} and Ruoyang Liu and Wang, \{Ya Nong\} and Yu Zhao",

note = "Publisher Copyright: {\textcopyright} 2018 Wiley-VCH Verlag GmbH \& Co. KGaA, Weinheim",

year = "2018",

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doi = "10.1002/anie.201804160",

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journal = "Angewandte Chemie - International Edition",

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T1 - Palladium-Titanium Relay Catalysis Enables Switch from Alkoxide-π-Allyl to Dienolate Reactivity for Spiro-Heterocycle Synthesis

AU - Yang, Li Cheng

AU - Tan, Zher Yin

AU - Rong, Zi Qiang

AU - Liu, Ruoyang

AU - Wang, Ya Nong

AU - Zhao, Yu

PY - 2018/6/25

Y1 - 2018/6/25

N2 - Reported herein is the divergent syntheses of [5,5] and [6,5] spiro-heterocycles under Lewis-acid-assisted palladium catalysis. In particular, an unprecedented switch from alkoxide-π-allyl to dienolate reactivity was achieved by the use of palladium-titanium relay catalysis, and represents umpolung reactivity of vinylethylene carbonates. This method uses a simple procedure and commercially available catalysts, and delivers both classes of spiro-heterocycles, bearing three contiguous stereocenters, in high yield and uniformly excellent diastereoselectivity.

AB - Reported herein is the divergent syntheses of [5,5] and [6,5] spiro-heterocycles under Lewis-acid-assisted palladium catalysis. In particular, an unprecedented switch from alkoxide-π-allyl to dienolate reactivity was achieved by the use of palladium-titanium relay catalysis, and represents umpolung reactivity of vinylethylene carbonates. This method uses a simple procedure and commercially available catalysts, and delivers both classes of spiro-heterocycles, bearing three contiguous stereocenters, in high yield and uniformly excellent diastereoselectivity.

KW - cycloaddition

KW - palladium

KW - relay catalysis

KW - spiro compounds

KW - umpolung

UR - https://www.scopus.com/pages/publications/85048830130

U2 - 10.1002/anie.201804160

DO - 10.1002/anie.201804160

M3 - Article

C2 - 29744984

AN - SCOPUS:85048830130

SN - 1433-7851

VL - 57

SP - 7860

EP - 7864

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 26

ER -

Palladium-Titanium Relay Catalysis Enables Switch from Alkoxide-π-Allyl to Dienolate Reactivity for Spiro-Heterocycle Synthesis

Abstract

Keywords

ASJC Scopus subject areas

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