Facile generation and isolation of φ-allyl complexes from aliphatic alkenes and an electron-deficient rh(III) complex: Key intermediates of allylic c-h functionalization

Yu Shibata, Eiji Kudo, Haruki Sugiyama, Hidehiro Uekusa, Ken Tanaka

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

It has been established that a strongly electrophilic ?5-cyclopentadienylrhodium complex, [CpERhCl2]2, is capable of reacting with aliphatic alkenes in the presence of a silver salt and cesium acetate at room temperature to give the corresponding ?-allyl complexes in high yields. The use of an alkenyltosylamide as the alkene also afforded the corresponding ?-allyl complex. Treatment of the thus obtained ?-allyl complex with a silver(I) salt and copper(II) acetate afforded the allylic amination product, which proves the intermediacy of this ?-allyl complex in the rhodium(III)-catalyzed intramolecular oxidative allylic amination.

Original languageEnglish
Pages (from-to)1547-1552
Number of pages6
JournalOrganometallics
Volume35
Issue number10
DOIs
Publication statusPublished - 2016 May 23
Externally publishedYes

Fingerprint

Amination
Alkenes
Silver
alkenes
acetates
isolation
Salts
silver
salts
Rhodium
Cesium
Electrons
rhodium
cesium
Acetates
electrons
copper
room temperature
products
Temperature

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Facile generation and isolation of φ-allyl complexes from aliphatic alkenes and an electron-deficient rh(III) complex : Key intermediates of allylic c-h functionalization. / Shibata, Yu; Kudo, Eiji; Sugiyama, Haruki; Uekusa, Hidehiro; Tanaka, Ken.

In: Organometallics, Vol. 35, No. 10, 23.05.2016, p. 1547-1552.

Research output: Contribution to journalArticle

Shibata, Yu ; Kudo, Eiji ; Sugiyama, Haruki ; Uekusa, Hidehiro ; Tanaka, Ken. / Facile generation and isolation of φ-allyl complexes from aliphatic alkenes and an electron-deficient rh(III) complex : Key intermediates of allylic c-h functionalization. In: Organometallics. 2016 ; Vol. 35, No. 10. pp. 1547-1552.
@article{2fc02d0a74874bf0affd7c706bc517e6,
title = "Facile generation and isolation of φ-allyl complexes from aliphatic alkenes and an electron-deficient rh(III) complex: Key intermediates of allylic c-h functionalization",
abstract = "It has been established that a strongly electrophilic ?5-cyclopentadienylrhodium complex, [CpERhCl2]2, is capable of reacting with aliphatic alkenes in the presence of a silver salt and cesium acetate at room temperature to give the corresponding ?-allyl complexes in high yields. The use of an alkenyltosylamide as the alkene also afforded the corresponding ?-allyl complex. Treatment of the thus obtained ?-allyl complex with a silver(I) salt and copper(II) acetate afforded the allylic amination product, which proves the intermediacy of this ?-allyl complex in the rhodium(III)-catalyzed intramolecular oxidative allylic amination.",
author = "Yu Shibata and Eiji Kudo and Haruki Sugiyama and Hidehiro Uekusa and Ken Tanaka",
year = "2016",
month = "5",
day = "23",
doi = "10.1021/acs.organomet.6b00143",
language = "English",
volume = "35",
pages = "1547--1552",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "10",

}

TY - JOUR

T1 - Facile generation and isolation of φ-allyl complexes from aliphatic alkenes and an electron-deficient rh(III) complex

T2 - Key intermediates of allylic c-h functionalization

AU - Shibata, Yu

AU - Kudo, Eiji

AU - Sugiyama, Haruki

AU - Uekusa, Hidehiro

AU - Tanaka, Ken

PY - 2016/5/23

Y1 - 2016/5/23

N2 - It has been established that a strongly electrophilic ?5-cyclopentadienylrhodium complex, [CpERhCl2]2, is capable of reacting with aliphatic alkenes in the presence of a silver salt and cesium acetate at room temperature to give the corresponding ?-allyl complexes in high yields. The use of an alkenyltosylamide as the alkene also afforded the corresponding ?-allyl complex. Treatment of the thus obtained ?-allyl complex with a silver(I) salt and copper(II) acetate afforded the allylic amination product, which proves the intermediacy of this ?-allyl complex in the rhodium(III)-catalyzed intramolecular oxidative allylic amination.

AB - It has been established that a strongly electrophilic ?5-cyclopentadienylrhodium complex, [CpERhCl2]2, is capable of reacting with aliphatic alkenes in the presence of a silver salt and cesium acetate at room temperature to give the corresponding ?-allyl complexes in high yields. The use of an alkenyltosylamide as the alkene also afforded the corresponding ?-allyl complex. Treatment of the thus obtained ?-allyl complex with a silver(I) salt and copper(II) acetate afforded the allylic amination product, which proves the intermediacy of this ?-allyl complex in the rhodium(III)-catalyzed intramolecular oxidative allylic amination.

UR - http://www.scopus.com/inward/record.url?scp=84971264124&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84971264124&partnerID=8YFLogxK

U2 - 10.1021/acs.organomet.6b00143

DO - 10.1021/acs.organomet.6b00143

M3 - Article

AN - SCOPUS:84971264124

VL - 35

SP - 1547

EP - 1552

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 10

ER -