Synthesis and Reactivity of Phosphine-Quinolinolato Rhodium Complexes: Intermediacy of Vinylidene and (Amino)carbene Complexes in the Catalytic Hydroamination of Terminal Alkynes

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

We report here on the syntheses of rhodium(I) complexes bearing a phosphine-quinolinolate ligand and the isolation of two classes of important intermediates in the anti-Markovnikov hydroamination of terminal alkynes with secondary amines: vinylidene-bridged dirhodium complexes and (amino)carbene complexes. We first prepared various rhodium(I) complexes bearing a phosphine-quinolinolate ligand and found that some of these complexes had catalytic activity for the anti-Markovnikov hydroamination of terminal alkynes with secondary amines. The reaction of stoichiometric amounts of a (PNO)Rh complex with terminal alkynes provided vinylidene-bridged dirhodium complexes. When the resulting vinylidene complexes were reacted with secondary amines, (amino)carbene complexes were generated, which gave the hydroamination product upon heating with an additive. These results suggest that this anti-Markovnikov hydroamination catalyzed by (PNO)Rh complexes proceeds via vinylidene and (amino)carbene complexes.

Original languageEnglish
Pages (from-to)4112-4125
Number of pages14
JournalOrganometallics
Volume35
Issue number24
DOIs
Publication statusPublished - 2016 Dec 27

Fingerprint

phosphine
Rhodium
Alkynes
carbenes
alkynes
Bearings (structural)
vinylidene
rhodium
phosphines
Amines
reactivity
amines
synthesis
Ligands
ligands
Catalyst activity
catalytic activity
Heating
isolation
heating

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

@article{35cf3111fdf84418b17fa83cdd46caf7,
title = "Synthesis and Reactivity of Phosphine-Quinolinolato Rhodium Complexes: Intermediacy of Vinylidene and (Amino)carbene Complexes in the Catalytic Hydroamination of Terminal Alkynes",
abstract = "We report here on the syntheses of rhodium(I) complexes bearing a phosphine-quinolinolate ligand and the isolation of two classes of important intermediates in the anti-Markovnikov hydroamination of terminal alkynes with secondary amines: vinylidene-bridged dirhodium complexes and (amino)carbene complexes. We first prepared various rhodium(I) complexes bearing a phosphine-quinolinolate ligand and found that some of these complexes had catalytic activity for the anti-Markovnikov hydroamination of terminal alkynes with secondary amines. The reaction of stoichiometric amounts of a (PNO)Rh complex with terminal alkynes provided vinylidene-bridged dirhodium complexes. When the resulting vinylidene complexes were reacted with secondary amines, (amino)carbene complexes were generated, which gave the hydroamination product upon heating with an additive. These results suggest that this anti-Markovnikov hydroamination catalyzed by (PNO)Rh complexes proceeds via vinylidene and (amino)carbene complexes.",
author = "Shotaro Takano and Takuya Kochi and Fumitoshi Kakiuchi",
year = "2016",
month = "12",
day = "27",
doi = "10.1021/acs.organomet.6b00853",
language = "English",
volume = "35",
pages = "4112--4125",
journal = "Organometallics",
issn = "0276-7333",
publisher = "American Chemical Society",
number = "24",

}

TY - JOUR

T1 - Synthesis and Reactivity of Phosphine-Quinolinolato Rhodium Complexes

T2 - Intermediacy of Vinylidene and (Amino)carbene Complexes in the Catalytic Hydroamination of Terminal Alkynes

AU - Takano, Shotaro

AU - Kochi, Takuya

AU - Kakiuchi, Fumitoshi

PY - 2016/12/27

Y1 - 2016/12/27

N2 - We report here on the syntheses of rhodium(I) complexes bearing a phosphine-quinolinolate ligand and the isolation of two classes of important intermediates in the anti-Markovnikov hydroamination of terminal alkynes with secondary amines: vinylidene-bridged dirhodium complexes and (amino)carbene complexes. We first prepared various rhodium(I) complexes bearing a phosphine-quinolinolate ligand and found that some of these complexes had catalytic activity for the anti-Markovnikov hydroamination of terminal alkynes with secondary amines. The reaction of stoichiometric amounts of a (PNO)Rh complex with terminal alkynes provided vinylidene-bridged dirhodium complexes. When the resulting vinylidene complexes were reacted with secondary amines, (amino)carbene complexes were generated, which gave the hydroamination product upon heating with an additive. These results suggest that this anti-Markovnikov hydroamination catalyzed by (PNO)Rh complexes proceeds via vinylidene and (amino)carbene complexes.

AB - We report here on the syntheses of rhodium(I) complexes bearing a phosphine-quinolinolate ligand and the isolation of two classes of important intermediates in the anti-Markovnikov hydroamination of terminal alkynes with secondary amines: vinylidene-bridged dirhodium complexes and (amino)carbene complexes. We first prepared various rhodium(I) complexes bearing a phosphine-quinolinolate ligand and found that some of these complexes had catalytic activity for the anti-Markovnikov hydroamination of terminal alkynes with secondary amines. The reaction of stoichiometric amounts of a (PNO)Rh complex with terminal alkynes provided vinylidene-bridged dirhodium complexes. When the resulting vinylidene complexes were reacted with secondary amines, (amino)carbene complexes were generated, which gave the hydroamination product upon heating with an additive. These results suggest that this anti-Markovnikov hydroamination catalyzed by (PNO)Rh complexes proceeds via vinylidene and (amino)carbene complexes.

UR - http://www.scopus.com/inward/record.url?scp=85008384505&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85008384505&partnerID=8YFLogxK

U2 - 10.1021/acs.organomet.6b00853

DO - 10.1021/acs.organomet.6b00853

M3 - Article

AN - SCOPUS:85008384505

VL - 35

SP - 4112

EP - 4125

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 24

ER -