1
484 Organometallics, Vol. 26, No. 6, 2007
Munro-Leighton et al.
In general, late transition metal catalysts exhibit greater
Cu(II)-catalyzed reactions with unactivated olefins have been
2
3,48-50
functional group tolerance than early transition metal systems
reported;
however, recent studies by Hartwig et al.
or lanthanide complexes.4
,6,8,22,23
The majority of late transition
suggest that metal-triflate catalysts may function through the
5
1
metal catalysts for olefin hydroamination are based on group
formation of triflic acid.
2,24-30
1
0 metals.2
For example, Tilley et al. have reported a Pt
Our group and others have been interested in the reactivity
of late transition metals with nondative heteroatomic ligands
(e.g., amido, hydroxide, alkoxide, etc.) and have shown these
catalyst for the Markovnikov addition of p-toluenesulfonamide
3
1
to olefins. Hartwig and co-workers have observed Pd(II)-
catalyzed Markovnikov addition of aniline to styrenes and vinyl
systems to exhibit nucleophilic and basic reactivity at the
32,33
52-68
naphthalenes including extension to enantioselective variants.
nondative functionality.
We have recently disclosed the
In addition, examples of ruthenium- and rhodium-catalyzed anti-
Markovnikov hydroaminations of vinylarenes have been re-
ported, although these catalytic cycles typically require the
addition of acid or result in formation of enamine byprod-
synthesis of monomeric Cu(I) complexes of the type (IPr)Cu-
(X) {IPr ) 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene;
X ) NHPh, OEt, or OPh} as well as (dtbpe)Cu(NHPh) {dtbpe
54,58,69
) 1,2-bis(di-tert-butylphosphino)ethane}.
Preliminary stud-
3
4,35
ucts.
ies indicate that these complexes catalyze the addition of amine
Though methods exist for the formation of ethers via catalytic
carbon-oxygen bond formation,36-39 examples of catalytic
hydroalkoxylation or hydroaryloxylation of olefins are relatively
scarce. Nonmetal systems include a phosphine-catalyzed hy-
droalkoxylation of electron-deficient olefins with alcohols and
an N-bromosuccinimide-catalyzed hydroalkoxylation of sty-
N-H bonds and alcohol O-H bonds across the carbon-carbon
69
double bonds of electron-deficient olefins. Herein, we report
on the scope of these reactions, including the impact of the
ancillary ligand “L” of (L)Cu(X) complexes where L ) IPr,
IMes, SIPr, or dtbpe {IMes ) 1,3-bis(2,4,6-trimethylphenyl)-
imidazol-2-ylidene; SIPr ) 1,3-bis(2,6-diisopropylphenyl)imi-
dazolin-2-ylidene; X ) NHPh, OEt, or OPh} on reactivity. The
series of Cu(I) systems studied are displayed in Chart 1.
4
0,41
renes.
Group 10 metals have proven effective for these
transformations as well, with published examples of Pd(0), Pd-
2-46
(
II), and Pt(II) catalysts.4
In addition, a Rh(I) catalyst and a
Ru(III) catalyst for intramolecular reactions have been re-
Results
ported.1
5,47
Au(I)-catalyzed olefin hydroamination and the
addition of O-H bonds to olefins, Cu(II)-catalyzed addition of
N-H bonds to electron-deficient olefins in ionic liquids, and
Catalytic Reactions of Amines Using (IPr)Cu(NHPh) (1).
Table 1 depicts results from Cu-catalyzed addition of N-H
bonds of amines across carbon-carbon double bonds of
electron-deficient olefins using (IPr)Cu(NHPh) (1) as catalyst.70
Control experiments conducted in the absence of Cu catalyst
confirm the role of the copper complexes in these reactions (see
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