Tunable Construction of Multisubstituted 1,3-Dienes and Allenes via a 1,4-Palladium Migration/Carbene Insertion Cascade

Jie Lin; Zilong Huang; Juan Ma; Bao Hua Xu; Yong Gui Zhou; Zhengkun Yu

doi:10.1021/acs.joc.2c01019

Tunable Construction of Multisubstituted 1,3-Dienes and Allenes via a 1,4-Palladium Migration/Carbene Insertion Cascade

Jie Lin
, Zilong Huang
, Juan Ma
, Bao Hua Xu
, Yong Gui Zhou^*
, Zhengkun Yu^*

^*Corresponding author for this work

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

19 Citations (Scopus)

Abstract

Efficient palladium-catalyzed vinylic C-H alkenylation and allenylation of gem-disubstituted ethylenes with N-tosylhydrazones of aryl alkyl and diaryl ketones were achieved to access trisubstituted 1,3-dienes and tetrasubstituted allenes, respectively. An aryl to vinyl 1,4-palladium migration/carbene insertion/β-hydride elimination sequence proceeded to switch the chemo- and regioselectivities to give structurally diverse products. Use of 2-FC₆H₄OH additive enables enhancement of the reaction efficiency through accelerating the key 1,4-palladium migration process.

Original language	English
Pages (from-to)	12019-12035
Number of pages	17
Journal	Journal of Organic Chemistry
Volume	87
Issue number	18
DOIs	https://doi.org/10.1021/acs.joc.2c01019
Publication status	Published - 16 Sept 2022
Externally published	Yes

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10.1021/acs.joc.2c01019

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title = "Tunable Construction of Multisubstituted 1,3-Dienes and Allenes via a 1,4-Palladium Migration/Carbene Insertion Cascade",

abstract = "Efficient palladium-catalyzed vinylic C-H alkenylation and allenylation of gem-disubstituted ethylenes with N-tosylhydrazones of aryl alkyl and diaryl ketones were achieved to access trisubstituted 1,3-dienes and tetrasubstituted allenes, respectively. An aryl to vinyl 1,4-palladium migration/carbene insertion/β-hydride elimination sequence proceeded to switch the chemo- and regioselectivities to give structurally diverse products. Use of 2-FC6H4OH additive enables enhancement of the reaction efficiency through accelerating the key 1,4-palladium migration process.",

author = "Jie Lin and Zilong Huang and Juan Ma and Xu, \{Bao Hua\} and Zhou, \{Yong Gui\} and Zhengkun Yu",

year = "2022",

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doi = "10.1021/acs.joc.2c01019",

language = "English",

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T1 - Tunable Construction of Multisubstituted 1,3-Dienes and Allenes via a 1,4-Palladium Migration/Carbene Insertion Cascade

AU - Lin, Jie

AU - Huang, Zilong

AU - Ma, Juan

AU - Xu, Bao Hua

AU - Zhou, Yong Gui

AU - Yu, Zhengkun

PY - 2022/9/16

Y1 - 2022/9/16

N2 - Efficient palladium-catalyzed vinylic C-H alkenylation and allenylation of gem-disubstituted ethylenes with N-tosylhydrazones of aryl alkyl and diaryl ketones were achieved to access trisubstituted 1,3-dienes and tetrasubstituted allenes, respectively. An aryl to vinyl 1,4-palladium migration/carbene insertion/β-hydride elimination sequence proceeded to switch the chemo- and regioselectivities to give structurally diverse products. Use of 2-FC6H4OH additive enables enhancement of the reaction efficiency through accelerating the key 1,4-palladium migration process.

AB - Efficient palladium-catalyzed vinylic C-H alkenylation and allenylation of gem-disubstituted ethylenes with N-tosylhydrazones of aryl alkyl and diaryl ketones were achieved to access trisubstituted 1,3-dienes and tetrasubstituted allenes, respectively. An aryl to vinyl 1,4-palladium migration/carbene insertion/β-hydride elimination sequence proceeded to switch the chemo- and regioselectivities to give structurally diverse products. Use of 2-FC6H4OH additive enables enhancement of the reaction efficiency through accelerating the key 1,4-palladium migration process.

UR - https://www.scopus.com/pages/publications/85137857661

U2 - 10.1021/acs.joc.2c01019

DO - 10.1021/acs.joc.2c01019

M3 - Article

AN - SCOPUS:85137857661

SN - 0022-3263

VL - 87

SP - 12019

EP - 12035

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

IS - 18

ER -

Tunable Construction of Multisubstituted 1,3-Dienes and Allenes via a 1,4-Palladium Migration/Carbene Insertion Cascade

Abstract

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