P-H activation using alkynylgold substrates: Steric and electronic effects

Article abstract of DOI:10.1039/c1dt11337b

The susceptibility of a prototypical hydrogen phosphonate to undergo P-H activation upon treatment with alkynylgold complexes has been studied. Dynamic solution behavior was observed during reactions involving triphenylphosphine ligated substrates and was attributed to rapid phosphine exchange between the alkynylgold starting material and the gold phosphonate product. The use of bulky biaryldialkylphosphine ligands eliminated the fluxional behavior, but did not significantly slow the rate of P-H activation. Similarly, changing the supporting ligand to an N-heterocyclic carbene did not significantly slow the rate of the reaction. Despite a number of reports outlining the functionalization of propargyl alcohols using gold catalysts, incorporating these groups into the architecture of the alkynylgold substrates did not alter the product distributions. Although the chemistry tolerated a range of supporting ligands, incorporating electron donating groups into the alkyne increased the rate of the reaction while electron-withdrawing groups slowed the reaction. A possible mechanism for the process includes a transition state containing significant pi-contribution from the alkyne. Due to the high yields of gold phosphonates obtained in this chemistry as well as the mild conditions of the reactions, the interception of intermediates/catalysts by substrates or ligands containing labile P-H donors is an issue that must be circumvented when designing or developing a gold catalyzed reaction that proceeds through alkynylgold intermediates. The Royal Society of Chemistry.

Full text of DOI:10.1039/c1dt11337b

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PAPER
P–H activation using alkynylgold substrates: steric and electronic effects†
Gerald F. Manbeck, Mark C. Kohler, Meghan R. Porter and Robert A. Stockland Jr.*
Received 15th July 2011, Accepted 6th September 2011
DOI: 10.1039/c1dt11337b
The susceptibility of a prototypical hydrogen phosphonate to undergo P–H activation upon treatment
with alkynylgold complexes has been studied. Dynamic solution behavior was observed during
reactions involving triphenylphosphine ligated substrates and was attributed to rapid phosphine
exchange between the alkynylgold starting material and the gold phosphonate product. The use of
bulky biaryldialkylphosphine ligands eliminated the fluxional behavior, but did not significantly slow
the rate of P–H activation. Similarly, changing the supporting ligand to an N-heterocyclic carbene did
not significantly slow the rate of the reaction. Despite a number of reports outlining the
functionalization of propargyl alcohols using gold catalysts, incorporating these groups into the
architecture of the alkynylgold substrates did not alter the product distributions. Although the
chemistry tolerated a range of supporting ligands, incorporating electron donating groups into the
alkyne increased the rate of the reaction while electron-withdrawing groups slowed the reaction. A
possible mechanism for the process includes a transition state containing significant pi-contribution
from the alkyne. Due to the high yields of gold phosphonates obtained in this chemistry as well as the
mild conditions of the reactions, the interception of intermediates/catalysts by substrates or ligands
containing labile P–H donors is an issue that must be circumvented when designing or developing a
gold catalyzed reaction that proceeds through alkynylgold intermediates.
catalyzed coupling of aryl triflates with Grignard reagents.26
Borner recently reported the use of hydrogen-phosphonates as
Introduction
ligands in rhodium catalyzed hydroformylation.24 Li and Shen
described the use of phosphine oxides as supporting ligands in
Suzuki couplings.27 Wolf outlined the use of phosphinous acid
containing complexes as catalysts for cross coupling aryl and acyl
halides with organozinc reagents.28
Defining the effects of steric and electronic manipulation on
the susceptibility of reagents, catalysts, and intermediates to
undergo a specific transformation provides critical structure
activity relationships. Furthermore, designing and developing new
approaches to the construction of carbon–carbon and carbon–
heteroelement bonds using gold complexes as catalysts has been
the subject of numerous investigations in recent years.1–8 While
many of these reactions utilize the “alkynophilic” nature of Au(I)
to activate alkynes through coordination of the metal center
to the p-system, a number of s-bound alkynylgold compounds
have been implicated as reactive intermediates in a range of
alkyne functionalizations.9–13 Recent examples include the gold
catalyzed ethynylation of activated arenes13 and the synthesis
of propargyl amines.10 Additionally, alkynylgold complexes are
efficient transmetallating agents and have been used in palladium
catalyzed cross coupling reactions as well as in the synthesis of
alkynylmetal species.14–19
One of the key concerns when using secondary phosphine oxides
or hydrogen phosphonates as substrates or ligands is the potential
for catalyst deactivation due to competing reactions between
these species and the organometallic catalysts/intermediates.29–40
Recently Waterman reported the reactivity of metal alkyls towards
primary phosphines.41 Treatment of a triamidoamine supported
zirconium species with PhPH2 activated one of the P–H bonds
and resulted in attachment of the phosphorus to the zirconium
center along with concomitant formation of methane. Schmidbaur
reported the generation of gold phosphonates by treatment of
methylgold complexes with hydrogen phosphonates.42 Our group
has reported the generation of bisphosphonate palladium com-
plexes upon addition of HP(O)(OR)2 species to alkylpalladium
phosphonates.43 Glueck recently described the tandem alkynyla-
tion/arylation of primary phosphines using platinum catalysts.
A key step in the catalytic reaction was a base-assisted reaction
of a primary phosphine with the platinum catalyst to generate a
platinum phosphide.44
The use of secondary phosphine oxides and hydrogen phos-
phonates as supporting ligands has grown in popularity in recent
years.20–25 Elegant work by Ackermann demonstrated that a hydro-
gen phosphonate served as a supporting ligand in the palladium
Department of Chemistry, Bucknell University, Lewisburg, Pennsylvania,
17837, USA. E-mail: rstockla@bucknell.edu
† Electronic supplementary information (ESI) available: NMR spectra for
all new compounds. See DOI: 10.1039/c1dt11337b
Due to its relevance towards the development of new
gold catalyzed reactions employing substrates containing labile
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Table 1 Synthesis of the alkynylgold compounds used in the P–H
tolerant of the bulky biaryldialkylphosphines as well as the SIMes
donor and moderate to high yields of the alkynylgold complexes
were obtained. While triphenylphosphine ligated examples were
successfully purified by multiple recrystallizations (pentane dif-
fusion into saturated benzene solutions), several of the SIMes,
JohnPhos, and tBuXPhos examples displayed significant solubility
in hexane and were purified by column chromatography. All of the
alkynylgold complexes were stable white solids with the exception
of the ferrocene containing species which were isolated as orange
crystals. In solution, the triphenylphosphine ligated compounds
activation reactions
1
displayed sharp singlets between 41–43 ppm in the 31P{ H} NMR
Comp.
Ligand
R
spectrum, while the JohnPhos and tBuXPhos ligated complexes
exhibited sharp resonances between 63 and 65 ppm. Compounds
containing the SIMes donor displayed the expected resonances
1
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
PPh3
JohnPhos
JohnPhos
JohnPhos
JohnPhos
JohnPhos
tBuXPhos
tBuXPhos
tBuXPhos
tBuXPhos
SIMes
SIMes
SIMes
SIMes
SIMes
SIMes
SIMes
SIMes
SIMes
SIMes
C6H5
4-C6H4Me
4-C6H4I
2
1
1
in the H and 13C{ H} NMR spectra with the carbene carbon
3
4
Ferrocene
(CH2)3Me
(CH2)2O-2-pyran
1-cyclohexene
CO2Et
Ethisterone
Cyclohexanol
C(OH)Me2
C(OH)H2
C6H5
(CH2)3Me
Ferrocene
C(OH)Me2
C(OH)H2
C6H5
(CH2)3Me
Ferrocene
Cyclohexanol
(CH2)3Me
4-C6H4Me
Ferrocene
Cyclohexene
(CH2)2O-2-pyran
CO2Me
observed between 209 and 211 ppm.
5
6
7
P–H activation studies
8
9
To determine a baseline for the reactivity of the alkynylgold
complexes towards HP(O)(OR)2 species, we investigated a model
system comprised of Ph3PAuC C–Bu (5) as the representative
alkynylgold complex and diethylphosphite as the prototypical
hydrogen phosphonate. During the initial phases of the project,
the effect of solvent on the rate and outcome of this reaction was
investigated. In CDCl3 solution, treatment of 5 with 1 equiv of
diethylphosphite (1.6 mM, 90 ◦C) smoothly generated the gold
phosphonate in near quantitative yields along with concomitant
formation of 1-hexyne. No attempts were made to remove the air
or adventitious moisture from these reactions.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
Preliminary concerns about side reactions between the alkynyl-
gold compounds and small amounts of acid from the CDCl3
were unwarranted. Only minimal amounts of Ph3PAuCl (<4%)
were observed after heating reactions in CDCl3 for several days.
Changing the solvent to C6D6 r◦esulted in a significant increase in
the rate of the reaction. At 90 C (in C6D6), the P–H activation
process was complete in a few minutes. Similar to the reactions in
CDCl3, only trace amounts of secondary products were observed.
Lowering the reaction temperature to 64 ◦C still afforded excellent
conversions in C6D6 solution.
Ethisterone
Cyclohexanol
C(OH)Me2
C(OH)H2
P–H bonds either as substrates or as supporting ligands, the
susceptibility of discrete alkynylgold complexes to promote
P–H activation has been determined. In addition, the electronic
and steric tolerance of the reaction has been established through
substrate and supporting ligand manipulation.
1
Monitoring the reaction by 31P{ H} NMR spectroscopy in
either CDCl3 or C6D6 revealed dynamic solution behavior dur-
ing the course of the reaction (Fig. 1). Although the isolated
alkynylgold species (5) displayed a sharp singlet in either CDCl3
or C6D6, significant broadening in the signal was observed upon
addition of diethylphosphite (~10 min). As the P–H activation
progressed, the signal for 5 continued to broaden and merged
with the phosphine resonance from Ph3PAuP(O)(OEt)2. Addi-
tionally, instead of the expected set of doublets, broad singlets
were observed. These collapsed doublets are likely to be the
result of phosphine exchange between the starting alkynylgold
species and the gold phosphonate. It was also possible that
the diethylphosphite tautomerized and coordinated/exchanged
with the triphenylphosphine bound to 5. However, the resonance
for the diethylphosphite was quite sharp while the signal for 5
broadened (Fig. 1) suggesting that it did not play a role in the
dynamic process. Another possibility was a reversible exchange
Results and discussion
Preparation of alkynylgold complexes
The alkynylgold substrates were prepared by treatment of LAuCl
(L = PPh3, JohnPhos, tBuXPhos, SIMes) precursors45–48 with
terminal alkynes and NaOH in CH2Cl2/MeOH (Table 1).49–51
A
variety of functionalized alkynes including propargyl alcohols
and steroids were successfully employed in these reactions. In
addition to changing the steric and electronic structure of the
alkynes, several different supporting ligands were incorporated
into the alkynylgold complexes. Bulky biaryldialkylphosphines
as well as an N-heterocyclic carbene (NHC) were also used
as donors for the gold center. This synthetic methodology was
process that generated (PPh3)2Au+ and Au(P(O)(OEt)2)2 . How-
-
ever, once the starting alkynylgold complex was fully consumed
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Table 2 P–H activation involving Ph3PAuC CR speciesa
alkynylgold complex
(Conv.) yieldb
(95)89
1
2
3
4
(94)87
(87)79
(88)81
5
6
(99)95
(91)83
7
8
(87)82
(40)
Fig. 1 Dynamic solution behavior observed while monitoring the P–H
activation involving complex 5 using 31P{ H} NMR spectroscopy (C6D6
1
a Reactions carried out in C6D6 (8.0 mM) at 64 ◦C under air. b Reaction
yields based upon isolated material. The numbers in parentheses represent
NMR conversions as determined using internal standards (anisole or
hexamethylbenzene).
at 64 ◦C). A) No diethylphosphite. B) 10 min. C) 14 h.
(or the gold phosphonate was isolated/purified), sharp doublets
for the two phosphorus centers in Ph3PAuP(O)(OEt)2 were
observed.
Once conditions for a successful P–H activation were found for
5, several functionalized alkynylgold species (1–8) were screened
in the NMR experiments (Table 2). The first manipulation of
the alkyne electronics involved changing the donating alkyl group
for slightly withdrawing aromatic groups (1–3). After stirring for
bulky ligands could inhibit the P–H activation process. Biaryl-
dialkylphosphine ligands were selected as the bulky phosphine
ligands (Tables 1 and 3) due to their remarkable air stability,53
ready availability,54 and propensity to promote transition metal
catalyzed cross coupling reactions.54–62
14 h at 64 ◦C, analysis of the 1H and 31P{ H} NMR spectra
Once isolated, the alkynylgold complexes incorporating bulky
phosphine ligands were screened in the P–H activation reac-
tion. Similar to the studies involving 1–8, diethylphosphite was
used as the prototypical P–H donor. The results of these P–
H activation studies are summarized in Table 3. Treatment of
13–15 and 18–20 with HP(O)(OEt)2 in C6D6 at 64 ◦C gener-
ated (JohnPhos)AuP(O)(OEt)2 and (tBuXPhos)AuP(O)(OEt)2 in
excellent yields. In contrast to the dynamic solution behavior
observed using triphenylphosphine as the supporting ligand
1
from reactions involving 1–3 revealed that slightly less of the
gold phosphonate had been formed (~80%). Heating the reaction
for an additional 5 h achieved >90% conversion. The ferrocene
derivative (4) also required slightly longer reaction times needed to
reach >90% conversion (~20 h).52 The most electron withdrawing
group screened in this chemistry was an ester (8). Incorporating
this group into the alkynylgold compound dramatically decreased
the◦rate of the P–H activation reaction. After stirring for 14 h at
64 C in C6D6, only 40% of 8 had been converted into the gold
phosphonate.
All of the triphenylphosphine ligated examples exhibited the
dynamic solution behavior described above. Correlating this data
revealed that alkyne substituents bearing electron donating groups
were more susceptible to P–H activation than those containing
electron withdrawing groups.
One of the issues with the P–H activation chemistry described
above was the dynamic solution behavior observed during the
course of the reaction. Eliminating this exchange process would
be ideal and one approach to slowing the intermolecular reaction
was to incorporate large bulky ligands around the gold center. In
addition to determining if these complexes slowed the exchange
process, they could also be used to probe whether or not
1
(Fig. 1) no broadening of the signals in the 1H or 31P{ H}
NMR spectra were observed in the reactions involving the bulky
biaryldialkylphosphines (Fig. 2). Thus, the addition of the bulky
ligands successfully inhibited the intermolecular exchange process
(at least on the NMR timescale). Analyzing the reaction data
revealed that the bulky phosphine ligands did not appear to
significantly impede the rate of P–H activation. High yields of
the gold phosphonates were obtained in virtually the same time
frame as when triphenylphosphine was used as the supporting
ligand.
In an effort to further explore the scope of this reaction,
an NHC ligand was incorporated into the alkynylgold com-
plexes. Carbenes are excellent s-donors and have been used
as supporting ligands for metal centers in a range of organic
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Table 3 P–H activation involving alkynylgold species containing bulky
groupsa
alkynylgold complex
gold phosphonate
(Conv.) yieldb
(98)89
1
2
(88)85
3
4
(89)78
(97)81
Fig. 2 No dynamic solution behavior observed while monitoring the P–H
1
activation involving complex 14 using 31P{ H} NMR spectroscopy (C6D6
at 64 ◦C). A) No diethylphosphite. B) 10 min. C) 14 h.
Adding electron withdrawing groups resulted in sluggish chemistry
and low conversions were observed. These results were similar
to the findings when compounds 1–8, 13–15, and 18–20 were
screened.
5
6
(95)80
(88)75
To investigate the functional group tolerance, model complexes
incorporating a range of propargyl alcohols were constructed
using the synthetic methodology described above. Reactions
involving these compounds could deviate significantly from the
clean P–H activation chemistry observed with LAuC CR (R =
alkyl, aryl) species as gold complexes are known to catalyze re-
actions involving propargyl alcohols.70–73 Furthermore, propargyl
alcohols react with a variety of compounds containing labile P–
H groups to generate a number of different products through
dehydration,74 substitution,75 and hydrophosphinylation.76,77 To
investigate whether or not the propargyl alcohol could circumvent
the P–H activation through alternate chemical reaction pathways
or inhibit the process by sequestering the phosphite through simple
hydrogen bonding, a range of alkynylgold complexes containing
triphenylphosphine (9–12), JohnPhos (16, 17), tBuXPhos (21),
and SIMes(28–31) were generated (Table 1) and screened for
reactivity towards diethylphosphite.
The alkynylgold complexes containing propargyl alcohols were
treated with diethylphosphite in C6D6 at 64 ◦C (Table 5). Despite
the potential for a range of products due to substitution, elimi-
nation, and addition, the propargyl alcohol containing substrates
underwent smooth P–H activation with no indication of secondary
reaction products. Furthermore, the identity of the groups at-
tached to the propargyl alcohol did not significantly affect the P–H
activation process. Complexes containing bulky steroids and 5–6
a Reactions carried out in C6D6 (8.0 mM) at 64 ◦C under air. b Reaction
yields based upon isolated material. The numbers in parentheses represent
NMR conversions as determined using internal standards (anisole or
hexamethylbenzene).
transformations.63–69 The alkynylgold species containing carbene
donors were generated using similar protocols to those described
above. Once in hand, the (SIMes)AuC CR complexes (22–27)
were treated with 1 equiv HP(O)(OEt)2 in C6D6 at 64 ◦C. In
most cases, treatment of these compounds with diethylphosphite
smoothly generated (SIMes)AuP(O)(OEt)2 in high yields (Table 4).
(SIMes)AuP(O)(OEt)2 was isolated as a white crystalline solid that
2
exhibited a JC–P of 170 Hz between the carbene carbon and the
phosphorus center. Similar to the approach used in the reactions
above, the electronic scope of the reaction was investigated by
changing the substituents attached to the alkyne. Incorporating
electron donating substituents resulted in the fastest reaction rates.
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Table 4 P–H activation involving (SIMes)AuC CR speciesa
Table 5 P–H activation using alkynylgold substrates containing propar-
gyl alcoholsa
alkynylgold complex
(Conv.) yieldb
alkynylgold complex
gold phosphonate (Conv.) yieldb
1
2
95
90
1
2
(95)
(90)
3
4
(89)85
(95)76
3
4
86
78
5
6
91c
(84)77
7
(93)90
5
6
87
8
9
95c
(88)75
(20)
10
(91)86
a Reactions carried out in C6D6 (8.0 mM) at 64 ◦C under air. b Conversion
based upon consumption of starting alkynylgold complex. Reaction yields
based upon isolated gold phosphonate.
11
89c
a Reactions carried out in C6D6 (8.0 mM) at 64 ◦C under air. b Reaction
yields based upon isolated material. The numbers in parentheses represent
NMR conversions as determined using internal standards (anisole or
hexamethylbenzene). c NMR conversions unavailable due to the low
solubility of the gold phosphonate.
membered rings were all converted into the corresponding gold
phosphonates. As shown in Table 5, changing from triphenylphos-
phine to a bulky biaryldialkylphosphine or a carbene did not have
a significant effect on the P–H activation process. Monitoring
the reaction mixtures using NMR spectroscopy revealed that
the triphenylphosphine ligated examples (9–12) exhibited the
same dynamic solution behavior observed with compounds 1–
8. Reactions involving the bulky biaryldialkylphosphine ligands
or SIMes did not exhibit any dynamic behavior and sharp signals
were observed in the NMR spectra. Thus, the P–H activation
proceeded without any inhibition due to the presence of the
propargyl alcohol.
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To probe the reactivity of the alkynylgold compounds towards
other hydrogen phosphonates, several additional substrates were
screened under the P–H activation conditions (eqn 1,2). Treatment
of (JohnPhos)AuC C–Ph and and (SIMes)AuC C-cyclohexan-
1-ol with cyclic hydrogen phosphonates (C6D6, 14 h) cleanly
generated the gold phosphonates in high yields. As with the
reactions involving diethylphosphite, the reaction chemistry was
very clean and only trace amounts of secondary products were
observed in these reactions.
designing or developing a gold catalyzed reaction that proceeds
through alkynylgold intermediates and involves hydrogen phos-
phonates as supporting ligands or substrates.
Experimental
General considerations
Diethyl ether, dichloromethane, THF, and hexane were dried
using a Grubbs-type solvent purification system. All reagents were
obtained from Acros and Aldrich and used as received with the
exception of diethylphosphite which was distilled twice before
use. Elemental analyses were performed by Midwest Microlabs.
NMR spectra were collected on a Varian 600 or 400 MHz NMR
spectrometer. 1H and 13C chemical shifts were determined by
reference to tetramethylsilane. 31P NMR spectra were referenced
relative to external phosphoric acid. All coupling constants are
given in hertz. The LAuCl (L = phosphine, SIMes) precursors
were prepared by displacement of dimethylsulfide from Me2AuCl
by added L, and their NMR spectra compared with literature
values.45–48 Known compounds 1, 2, 4, 5, 9, 10, and 12 were
prepared following the general procedures outlined below, and
their NMR spectra compared with reported literature values (see
ESI†).78,81–84
(1)
(2)
General procedure for preparation of alkynyl gold complexes45–48
.
A round bottom flask (50 mL) was charged with the LAuX
(X = Cl; L = PPh3, JohnPhos, tBuXPhos, SIMes) precursor,
and 2 equiv of NaOH. After evacuating and refilling the flask
with nitrogen, methanol (10 mL) was added by syringe, and
the reaction mixture was stirred for 20 min. Dichloromethane
was added until a homogeneous solution was obtained. Liquid
alkynes were added directly to this solution while solid alkynes
were dissolved in MeOH/CH2Cl2 prior to addition. The reaction
was covered in foil and stirred overnight followed by removal of
the volatiles under vacuum and extraction of the residue with
benzene (10 mL). After filtration to remove insoluble salts, the
desired alkynylgold complexes were purified by recrystallization
or column chromatography
There are several possibilities for the mechanism of this
reaction. One possibility entails oxidative addition of the P–
H bond across the gold center to generate a gold(III) species.
Reductive elimination would afford the observed products. Our
own attempts to effect an oxidative addition reaction between aryl
halides and gold substituted ethynylsteroids78 were unsuccessful
and only starting materials were recovered. These observations
were supported by a recent report which outlined problematic
oxidative addition reactions of aryl halides to gold(I) centers.17 The
electronic effects observed in these reactions suggest the presence
of a transition state containing coordination of the P–H donor to
the metal complex such that there is partial overlap of the alkyne p-
system while simultaneously labilizing the gold–carbon bond.79,80
Electron donating groups would enhance this p-contribution and
accelerate the reaction while electron withdrawing groups would
result in sluggish P–H activation.
Preparation of 3. The general procedure was followed with
Ph3PAuCl (0.20 g, 0.404 mmol), 4-iodoethynylbenzene (0.093 g,
0.408 mmol), NaOH (0.032 g, 0.80 mmol), CH2Cl2 (5 mL), and
MeOH (10 mL). Recrystallization by diffusion of pentane into
a saturated benzene solution afforded 0.18 g (64.9%) of the title
compound as white needles. Anal. Calcd for C26H19AuIP: C, 45.50;
Conclusions
H, 2.79. Found: C, 45.13; H, 3.42. H NMR (CDCl3, 25 ◦C):
1
Discrete alkynylgold complexes react with hydrogen phosphonates
under mild conditions to generate gold phosphonates and a
terminal alkyne through P–H activation. The chemistry tolerated
a wide range of functional groups including propargyl alcohols.
Increasing the steric bulk of the supporting ligand did not
significantly inhibit or change the outcome of the reactions. A
significant electronic effect was found and correlated with the
identity of the organic fragment on the alkyne. Electron donating
substituents exhibited faster rates while substrates containing
electron withdrawing groups were sluggish under the reaction
conditions. Due to the high yields of gold phosphonates obtained
in this chemistry as well as the mild conditions of the reactions,
the interception of intermediates/catalysts by reagents containing
labile P–H donors is an issue that must be circumvented when
d 7.58–7.49 (m, 11H, Ar–H), 7.48–7.43 (m, 6H, Ar–H), 7.22
◦
1
(AA¢BB¢, 2H, Ar–H).13C{ H} NMR (CDCl3, 25 C): d 137.1 (s,
Ar–CH), 134.3 (d, J = 13.4, Ar–CH), 133.8 (d, J = 142.1, C–),
134.0 (s, Ar–CH), 131.6 (d, J = 2.9, Ar–CH), 129.7 (d, J = 56.1,
quat), 129.2 (d, J = 11.2, Ar–CH), 124.4 (d, J = 2.9, quat), 103.1
◦
1
(d, J = 26.2, C–), 92.2 (s, quat). 31P{ H} NMR (CDCl3, 25 C):
d 42.2 (s).
Preparation of 6. The general procedure was followed with
Ph3PAuCl (0.20 g, 0.404 mmol), 2-(3-butynyloxy)tetrahydro-2H-
pyran (48 mL, 0.408 mmol), NaOH (0.032 g, 0.80 mmol), CH2Cl2
(5 mL), and MeOH (10 mL). Recrystallization by diffusion
of pentane into a saturated benzene solution afforded 0.21 g
(84.8%) of the title compound as white needles. Anal. Calcd for
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1
C27H28AuO2P: C, 52.95; H, 4.61. Found: C, 52.58; H, 4.38. H
0.19 g (84.5%) of a white powder. Anal. Calcd for C28H32AuP:
NMR (CDCl3, 25 ◦C): d 7.54–7.47 (m, 9H, –C6H5), 7.44–7.41 (m,
6H, –C6H5), 4.65 (t, 1H, J = 4.0, –CH–), 3.88 (m, 2H, –CH2–),
3.66 (m, 1H, –CH2–), 3.49 (m, 1H, –CH2–), 2.70 (t, 2H, J = 7.8,
–CH2–), 1.83 (m, 1H, –CH2–), 1.71 (m, 1H, –CH2–), 1.61–1.49 (m,
C, 56.38; H, 5.41. Found: C, 56.45; H, 5.40. H NMR (CDCl3,
1
25 ◦C): d 7.87 (m, 1H, Ar–CH), 7.56–7.44 (m, 7H, Ar–CH), 7.29
(m, 1H, Ar–CH), 7.24–7.14 (m, 5H, Ar–CH)◦, 1.42 (d, 18H, J =
1
14.4, –PC(CH3)3). 13C{ H} NMR (CDCl3, 25 C): d 150.3 (d, J =
◦
1
4H, –CH2–).13C{ H} NMR (CDCl3, 25 C): d 134.3 (d, J = 13.6,
–C6H5), 131.5 (d, J = 2.3, –C6H5), 129.9 (d, J = 55.5, –ipso–C6H5),
129.1 (d, J = 11.2, –C6H5), 121.1 (d, J = 142.2, C–), 101.2 (d,
J = 27.0, C–), 98.7 (s, –CH–), 67.0 (s, –CH2–), 62.2 (s, –CH2–),
30.6 (s, –CH2–), 25.5 (s, –CH2–), 21.◦3 (d, J = 2.3, –CH2–), 19.6 (s,
15.2, quat), 142.4 (d, J = 6.2, quat), 134.3 (d, J = 1.2, Ar–CH),
134.1 (d, J = 131.8, C–), 133.1 (d, J = 7.2, Ar–CH), 132.2 (s,
Ar–CH), 130.2 (d, J = 2.3, Ar–CH), 129.2 (s, Ar–CH), 129.0 (s,
Ar–CH), 128.1 (s, Ar–CH), 127.7 (s, Ar–CH), 127.6 (d, J = 39.8,
quat), 126.6 (d, J = 5.6, Ar–CH), 126.2 (d, J = 2.7, quat), 126.0 (s,
Ar–CH), 102.2 (d, J = 23.5, C–), 37.5 (d, J = 22.3, PC(CH3)3),
–CH2–). 31P{ H} NMR (CDCl3, 25 C): d 42.3 (s).
1
◦
1
31.1 (d, J = 7.2, PC(CH3)3). 31P{ H} NMR (CDCl3, 25 C): d 64.4
Preparation of 7. The general procedure was followed with
(Ph3P)AuCl (0.20 g, 0.404 mmol), 1-ethynylcyclohexene (47.6 mL,
0.405 mmol), NaOH (0.032 g, 0.80 mmol), CH2Cl2 (5 mL), and
MeOH (10 mL). Recrystallization by diffusion of pentane into
a saturated benzene solution afforded 0.15 g (65.7%) of the title
compound as white needles. Anal. Calcd for C26H24AuP: C,◦55.33;
(s).
Preparation of 14. The general procedure was followed with
(JohnPhos)AuCl (0.20 g, 0.377 mmol), 1-hexyne (43.3 ml, 0.377
mmol), NaOH (0.030 g, 0.75 mmol), CH2Cl2 (5 mL), and
MeOH (10 mL). The title compound was purified by column
chromatography (THF/hexane gradient 10 : 90–60 : 40) to afford
0.16 g (73.7%) of a white powder. Anal. Calcd for C26H36AuP: C,
54.17; H, 6.29. Found: C, 54.29; H, 6.25. 1H NMR (CDCl3, 25 ◦C):
d 7.84 (m, 1H, Ar–H), 7.45 (m, 5H, Ar–H), 7.26 (m, 1H, Ar–H),
7.14 (m, 2H, Ar–H), 2.26 (m, 2H, –CH2–), 1.55 (m, 2H, –CH2–),
1.48 (m, 2H, –CH2–), 1.39 (d, 18H, J = 14.9, PC(CH3)3), 0.96 (t,
1
H, 4.29. Found: C, 55.61; H, 4.57. H NMR (CDCl3, 25 C): d
7.55–7.48 (m, 9H, –C6H5), 7.44–7.42 (m, 6H, –C6H5), 6.13 (m, 1H,
CH–), 2.21 (m, 2H, –CH2–), 2.09 (m, 2H, –CH2–), 1.62 (m, 2H,
◦
1
–CH2–), 1.56 (m, 2H, –CH2–). 13C{ H} NMR (CDCl3, 25 C): d
134.4 (d, J = 13.6, –C6H5), 133.5 (s, CH–), 131.5 (d, J = 2.7,
–C6H5), 129.9 (d, J = 55.6, –ipso–C6H5), 129.1(d, J = 11.3, –C6H5),
127.8 (d, J = 141.9, C–), 121.3 (s, quat), 106.5 (d, J = 26.2,
C–), 30.4 (s, –CH2–), 25.8 (s, –CH2–), 22.6 (s, –CH2–), 21.7 (s,
◦
3H, J = 7.5, –CH3). 13C{ H} NMR (CDCl3, 25 C): d 150.4 (d,
J = 15.2, quat), 142.4 (d, J = 6.2, quat), 134.4 (d, J = 1.1, Ar–CH),
133.0 (d, J = 7.2, Ar–CH), 130.1 (d, J = 2.1, Ar–CH), 129.2 (s,
Ar–CH), 128.9 (s, Ar–CH), 128.0 (s, Ar–CH), 127.7 (d, J = 38.8,
quat), 126.5 (d, J = 6.2, Ar–CH), 120.4 (d, J = 131.8, C–), 103.0
(d, J = 23.5, C–), 37.4 (d, J = 22.5, PC(CH3)3), 32.4 (s, –CH2–),
31.0 (d, J = 7.2, PC(CH3)3), 22.3 (s, –CH2–), 19.9 (d, J = 2.3,
1
◦
–CH2–).31P{ H} NMR (CDCl3, 25 C): d 42.4 (s).
1
Preparation of 8. The general procedure was followed with
Ph3PAuCl (0.20 g, 0.404 mmol), ethylpropiolate (41 mL, 0.405
mmol), NaOH (0.032 g, 0.80 mmol), CH2Cl2 (5 mL), and EtOH
(10 mL). Recrystallization by diffusion of pentane into a saturated
benzene solution afforded 0.14 g (62.2%) of the title compound
as white needles. Anal. Calcd for C23H20AuO2P: C, 49.65; H, 3.62.
Found: C, 49.88; H, 3.15. 1H NMR (CDCl3, 25 ◦C): d 7.55–7.43
(m, 15H, Ar–H), 4.20 (q, 2H, J = 7.0, –OCH2–), 1.29 (t, 3H, J =
◦
1
–CH2–), 13.9 (s, –CH3). 31P{ H} NMR (CDCl3, 25 C): d 64.4 (s).
Preparation of 15. The general procedure was followed with
(JohnPhos)AuCl (0.20 g, 0.377 mmol), ethynylferrocene (0.08 g,
0.381 mmol), NaOH (0.030 g, 0.75 mmol), CH2Cl2 (5 mL), and
MeOH (10 mL). The title compound was purified by column
chromatography (THF/hexane gradient 10 : 90–60 : 40) to afford
0.23 g (86.7%) of an orange powder. Anal. Calcd for C32H36AuFeP:
◦
1
7.1, –CH3). 13C{ H} NMR (CDCl3, 25 C): d 153.5 (d, J = 2.9,
C
O), 134.3 (d, J = 141.3, C–), 134.3 (d, J = 14.0, –C6H5),
131.8 (d, J = 2.3, –C6H5), 129.3 (d, J = 11.8, –C6H5), 129.2 (d, J =
57.2, ipso–C6H5), 93.6 (d, J = 25.8, C–), 61.2 (s, –OCH2–), 14.2
1
C, 54.56; H, 5.15. Found: C, 54.74; H, 4.99. H NMR (CDCl3,
◦
1
(s, –CH3). 31P{ H} NMR (CDCl3, 25 C): d 41.3 (s).
25 ◦C): d 7.85 (m, 1H, Ar–H), 7.58 (m, 1H, Ar–H), 7.51–7.42 (m,
4H, Ar–H), 7.27 (m, 1H, Ar–H), 7.18 (m, 2H, Ar–H), 4.37 (m, 2H,
Ar–H), 4.22 (s, 5H, Ar–H), 4.06 (m, 2H, Ar–H), 1.41 (d, 18H, J =
Preparation of 11. The general procedure was followed with
PPh3AuCl (0.20 g, 0.404 mmol), 2-methyl-3-butyn-2-ol (39.2 mL,
0.404 mmol), NaOH (0.032 g, 0.80 mmol), CH2Cl2 (5 mL), and
MeOH (10 mL). Recrystallization by diffusion of pentane into a
saturated benzene/CH2Cl2 solution afforded 0.13 g (59.3%) of the
title compound as white needles. Anal. Calcd for C23H22AuOP:
◦
1
14.9, PC(CH3)3). 13C{ H} NMR (CDCl3, 25 C): d 150.3 (d, J =
15.7, quat), 142.4 (d, J = 6.2, quat), 134.4 (s, Ar–CH), 133.1 (d, J =
7.2, Ar–CH), 130.1 (d, J = 3.2, Ar–CH), 130.1 (d, J = 132.4, C–),
129.3 (s, Ar–CH), 129.0 (s, Ar–CH), 128.0 (s, Ar–CH), 127.7 (d,
J = 39.2, quat), 126.5 (d, J = 5.6, Ar–CH), 99.2 (d, J = 23.5, C–),
71.6 (s, CH), 69.8 (s, CH), 69.5 (d, J = 2.9, quat), 67.3 (s,
CH), 37.4 (d, J = 22.3, PC(CH3)3), 31.1 (d, J = 7.2, PC(CH3)3).
1
C, 50.93; H, 4.09. Found: C, 50.92; H, 4.08. H NMR (CDCl3,
◦
25 C): d 7.55–7.48 (m, 9H, –C6H5), 7.46–7.4◦2 (m, 6H, –C6H5),
1
1.59 (s, 6H, –CH3). 13C{ H} NMR (CDCl3, 25 C): d 134.3 (d, J =
◦
1
31P{ H} NMR (CDCl3, 25 C): d 64.5 (s).
14.0, –C6H5), 131.5 (d, J = 2.3, –C6H5), 129.8 (d, J = 54.9, quat),
129.1 (d, J = 11.3, –C6H5), 121.3 (d, J = 141.6, C–), 109.5 (d, J =
Preparation of 16. The general procedure was followed with
(JohnPhos)AuCl (0.20 g, 0.377 mmol), 2-methyl-3-butyn-2-ol
(36.8 ml, 0.380 mmol), NaOH (0.030 g, 0.75 mmol), CH2Cl2 (5 mL),
and MeOH (10 mL). The title compound was purified by column
chromatography (THF/hexane gradient 10 : 90–60 : 40) to afford
0.19 g (87.2%) of a white powder. Anal. Calcd for C25H34AuOP:
1
25.5, C–), 65.6 (s, quat), 32.6 (s, –CH3). 31P{ H} NMR (CDCl3,
25 ◦C): d 42.3 (s)
Preparation of 13. The general procedure was followed with
(JohnPhos)AuCl (0.20 g, 0.377 mmol), phenylacetylene (41.4 mL,
0.377 mmol), NaOH (0.030 g, 0.75 mmol), CH2Cl2 (5 mL), and
MeOH (10 mL). The title compound was purified by column
chromatography (THF/hexane gradient 10 : 90–60 : 40) to afford
1
C, 51.91; H, 5.92. Found: C, 51.65; H, 6.12. H NMR (CDCl3,
◦
25 C): d 7.85 (t, 1H, J = 7.8, Ar–H), 7.51–7.44 (m, 5H, Ar–H),
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7.26 (m, 1H, Ar–H), 7.15 (m, 2H, Ar–H), 1.96 (s, 1H, OH), 1.56 (s,
Ar–H), 7.07 (s, 2H, Ar–H), 2.97 (sept, 1H, J = 6.9, iPr–CH), 2.34
(sept, 2H, J = 6.9, Pr–CH), 2.17 (m, 2H, –CH2–), 1.47 (m, 2H,
1
i
6H, –CH3), 1.39 (d, 18H, J = 15.0, –CH3). 13C{ H} NMR (CDCl3,
25 ◦C): d 150.3 (d, J = 15.2, quat), 142.5 (d, J = 6.2, quat), 134.3
(d, J = 1.1, Ar–H), 133.1 (d, J = 7.2, Ar–H), 130.2 (d, J = 2.3,
Ar–H), 129.2 (s, Ar–H), 128.9 (s, Ar–H), 127.9 (s, Ar–H), 127.6
(d, J = 39.8, quat), 126.6 (d, J = 5.6, Ar–H), 123.1 (d, J = 131.4,
C–), 107.0 (d, J = 22.5, C–), 65.5 (d, J = 1.7, quat), 37.4 (d,
J = 22.5, PC(CH3)3), 32.7 (◦s, –CH3), 31.0 (d, J = 6.6, PC(CH3)3).
–CH2–), 1.38 (d, 18H, J = 14.4, –C(CH3)3), 1.37 (m, 2H, –CH2–),
1.36 (d, 6H, J = 7.2, iPr–CH3), 1.31 (d, 6H, J = 7.2, iPr–CH3), 0.90
i
1
(d, 6H, J = 7.0, Pr–CH3), 0.89 (t, 3H, J = 7.2, –CH3). 13C{ H}
NMR (CDCl3, 25 ◦C): d 149.1 (s, quat), 148.5 (d, J = 15.7, quat),
145.5 (s, quat), 135.7 (d, J = 5.1, quat), 135.3 (d, J = 1.7, CH–),
134.7 (d, J = 7.8, CH–), 129.8 (d, J = 35.9, quat), 129.6 (d, J =
2.1, CH–), 126.0 (d, J = 5.6, CH–), 121.8 (s, CH–), 121.4
(d, J = 133.5, C–), 101.8 (d, J = 24.1, C–), 38.0 (d, J = 23.1,
1
31P{ H} NMR (CDCl3, 25 C): d 64.5 (s).
Preparation of 17. The general procedure was followed with
(JohnPhos)AuCl (0.20 g, 0.377 mmol), propargyl alcohol (22.0 mL,
0.380 mmol), NaOH (0.030 g, 0.75 mmol), CH2Cl2 (5 mL), and
MeOH (10 mL). The title compound was purified by column
chromatography (THF/hexane gradient 10 : 90–60 : 40) to afford
0.13 g (62.7%) of a white powder. Anal. Calcd for C23H30AuOP:
i
PC(CH3)3), 34.0 (s, Pr–CH), 32.3 (s, –CH2–), 31.4 (d, J = 6.8,
PC(CH3)3), 30.8 (s, iPr–CH), 26.3 (s, iPr–CH3), 24.0 (s, iPr–CH3),
22.9 (s, iPr–CH3), 22.3 (s, –CH2–), 20◦.1 (d, J = 2.3, –CH2–), 13.8
(s, –CH3). 31P{ H} NMR (CDCl3, 25 C): d 64.1 (s).
1
Preparation of 20. The general procedure was followed with
(tBuXPhos)AuCl (0.20 g, 0.304 mmol), ethynylferrocene (0.065 g,
0.309 mmol), NaOH (0.025 g, 0.625 mmol), CH2Cl2 (5 mL), and
MeOH (10 mL). The title compound was purified by column
chromatography (THF/hexane gradient 10 : 90–60 : 40) to afford
0.22 g (87.0%) of an orange powder. Anal. Calcd for C41H54AuFeP:
1
C, 50.19; H, 5.49. Found: C, 49.80; H, 5.72. H NMR (CDCl3,
25 ◦C): d 7.85 (m, 1H, Ar–H), 7.51–7.40 (m, 5H, Ar–H), 7.28
(m, 1H, Ar–H), 7.15 (m, 2H, Ar–H), 4.31 (dd, 2H, J = 6.0, 1.2,
C(OH)H2), 1.40 (d, 18H, J = 15.0, PC(CH3)3), 1.36 (t, 1H, J =
◦
1
6.0, C(OH)H2). 13C{ H} NMR (CDCl3, 25 C): d 150.2 (d, J =
15.1, quat), 142.5 (d, J = 6.2, quat), 134.3 (d, J = 1.2, Ar–CH),
133.1 (d, J = 7.2, Ar–CH), 130.3 (d, J = 2.3, Ar–CH), 129.2 (s,
Ar–CH), 128.9 (s, Ar–CH), 128.1 (d, J = 130.1, C–), 127.9 (s,
Ar–CH), 127.4 (d, J = 39.8, quat), 126.6 (d, J = 5.7, Ar–CH), 100.5
(d, J = 22.9, C–), 52.2 (d, J = 2.3, C(OH)H2), 37.5 (d, J = 22.5,
1
C, 59.28; H, 6.55. Found: C, 59.64; H, 6.36. H NMR (CDCl3,
25 ◦C): d 7.89 (m, 1H, Ar–H), 7.49–7.42 (m, 2H, Ar–H), 7.29 (m,
1H, Ar–H), 7.13 (s, 2H, Ar–H), 4.31 (m, 2H, CH), 4.18 (m, 5H,
CH), 4.03 (m, 2H, CH), 3.08 (sept, 1H, J = 6.8, iPrCH), 2.38
(sept, 2H, J = 6.8, iPrCH), 1.43 (d, 6H, J = 6.6, iPr–CH3), 1.43 (d,
18H, J = 15.0, PC(CH3)3), 1.37 (d, 6H, J = 6.6, iPr–CH3), 0.93 (d,
1
PC(CH3)3), 31.0 (d, J = 6.6, PC(CH3)3). 31P{ H} NMR (CDCl3,
25 ◦C): d 64.1 (s).
◦
1
6H, J = 6.6, iPr–CH3). 13C{ H} NMR (CDCl3, 25 C): d 149.2 (s,
quat), 148.5 (d, J = 15.8, quat), 145.6 (s, quat), 135.7 (d, J = 5.0,
quat), 135.3 (d, J = 1.1, Ar–CH), 134.7 (d, J = 8.0, Ar–CH), 131.3
(d, J = 134.1, C–), 129.6 (d, J = 36.5, quat), 129.6 (d, J = 2.1,
Ar–CH), 126.1 (d, J = 5.7, Ar–CH), 121.9 (s, Ar–CH), 98.4 (d, J =
24.6, C–), 71.5 (s, CH), 70.0 (d, J = 2.9, quat), 69.8 (s, CH),
67.1 (s, CH), 38.1 (d, J = 23.1, PC(CH3)3), 34.1 (s, iPrCH), 31.5
(d, J = 6.8, PC(CH3)3), 30.9 (s, iPrCH), 26.3 (s, iPr–CH3), 24.4 (s,
Preparation of 18. The general procedure was followed with
(tBuXPhos)AuCl (0.20 g, 0.304 mmol), phenylacetylene (33.5 ml,
0.305 mmol), NaOH (0.025 g, 0.625 mmol), CH2Cl2 (5 mL), and
MeOH (10 mL). The title compound was purified by column
chromatography (THF/hexane gradient 10 : 90–60 : 40) to afford
0.16 g (72.7%) of a white powder. Anal. Calcd for C37H50AuP:
1
C, 61.49; H, 6.97. Found: C, 61.36; H, 6.37. H NMR (CDCl3,
◦
1
◦
iPr–CH3), 23.1 (s, iPr–CH3). 31P{ H} NMR (CDCl3, 25 C): d 64.0
25 C): d 7.89 (m, 1H, Ar–CH), 7.45 (m, 2H, Ar–CH), 7.38 (m,
(s).
2H, Ar–CH), 7.31 (m, 1H, Ar–CH), 7.18 (m, 2H, Ar–CH), 7.11
(m, 3H, Ar–CH), 2.92 (sept, 1H, J = 6.9, iPr–CH), 2.38 (sept, 2H,
J = 6.6, iPr–CH), 1.43 (d, 18H, J = 15.0, PC(CH3)3), 1.36 (d, 6H,
Preparation of 21. The general procedure was followed with
(tBuXPhos)AuCl (0.20 g, 0.304 mmol), 1-ethynyl-1-cyclohexanol
(0.038 g, 0.306 mmol), NaOH (0.025 g, 0.625 mmol), CH2Cl2
(5 mL), and MeOH (10 mL). The title compound was purified by
column chromatography (THF/hexane gradient 10 : 90–60 : 40)
to afford 0.21 g (92.6%) of a white powder. Anal. Calcd for
J = 7.2, iPr–CH3), 1.26 (d, 6H, J = 7.2, iPr–CH3), 0.93 (d, 6H, J =
◦
i
1
6.6, Pr–CH3). 13C{ H} NMR (CDCl3, 25 C): d 149.4 (s, quat),
148.6 (d, J = 15.7, quat), 145.6 (s, quat), 135.7 (d, J = 2.0, quat),
135.5 (d, J = 132.9, C–), 135.3 (d, J = 1.7, Ar–CH–), 134.7 (d,
J = 7.8, Ar–CH–), 132.2 (d, J = 1.1, Ar–CH–), 129.7 (d, J = 1.8,
Ar–CH–), 129.5 (s, quat), 127.5 (s, Ar–CH–), 126.7 (d, J = 2.3,
quat), 126.1 (d, J = 6.2, Ar–CH–), 125.5 (s, Ar–CH–), 121.9 (s,
Ar–CH–), 101.6 (d, J = 23.5, C–), 38.1 (d, J = 22.9, PC(CH3)3),
33.9 (s, iPrCH–), 31.4 (d, J = 6.6, PC(CH3)3), 30.9 (s, iPrCH–), 26.3
1
C37H56AuOP: C, 59◦ .67; H, 7.58. Found: C, 59.40; H, 7.35. H
NMR (CDCl3, 25 C): d 7.88 (m, 1H, Ar–H), 7.44 (m, 2H, Ar–
H), 7.27 (m, 1H, Ar–H), 7.08 (s, 2H, Ar–H), 2.99 (sept, 1H, J =
i
i
6.9, PrCH), 2.35 (sept, 2H, J = 6.8, PrCH), 1.88 (s, 1H, –OH),
1.83 (m, 2H, –CH2–), 1.64 (m, 4H, –CH2–), 1.56 (m, 2H, –CH2–),
1.46 (m, 1H, –CH2–), 1.41 (d, 18H, J = 14.7, PC(CH3)3), 1.37 (d,
6H, J = 6.8, iPr–CH3), 1.32 (d, 6H, J = 6.8, iPr–CH3), 1.27 (m, 1H,
(s, iPr–CH3), 24.0 (s, iPr–CH3), 23.0 (s, iPr–CH3). 31P{ H} NMR
1
(CDCl3, 25 ◦C): d 63.1 (s).
i
1
Preparation of 19. The general procedure was followed with
(tBuXPhos)AuCl (0.20 g, 0.304 mmol), 1-hexyne (35.0 ml, 0.305
mmol), NaOH (0.025 g, 0.625 mmol), CH2Cl2 (5 mL), and
MeOH (10 mL). The title compound was purified by column
chromatography (THF/hexane gradient 10 : 90–60 : 40) to afford
0.15 g (70.1%) of a white powder. Anal. Calcd for C35H54AuP:
–CH2–), 0.91 (d, 6H, J = 6.5, Pr–CH3). 13C{ H} NMR (CDCl3,
25 ◦C): d 149.1 (s, quat), 148.5 (d, J = 15.7, quat), 145.6 (s, quat),
135.8 (d, J = 5.1, quat), 135.3 (d, J = 1.7, Ar–CH), 134.8 (d, J =
7.8, Ar–CH), 129.7 (d, J = 2.3, Ar–CH), 129.5, (d, J = 36.5, quat),
126.2 (d, J = 132.4, C–), 126.1 (d, J = 5.6, Ar–CH), 121.8 (s,
Ar–CH), 105.4 (d, J = 22.3, C–), 68.9 (s, quat), 41.0 (s, –CH2–),
1
i
C, 59.82; H, 7.75. Found: C, 59.44; H, 8.01. H NMR (CDCl3,
38.1 (d, J = 23.1, PC(CH3)3), 34.1 (s, Pr–CH), 31.4 (d, J = 6.6,
25 ◦C): d 7.86 (m, 1H, Ar–H), 7.42 (m, 2H, Ar–H), 7.27 (m, 1H,
12602 | Dalton Trans., 2011, 40, 12595–12606
PC(CH3)3), 30.9 (s, Pr–CH), 26.3 (s, Pr–CH3), 25.7 (s, –CH2–),
i
i
This journal is The Royal Society of Chemistry 2011
©

View Article Online
1
24.3 (s, iPr–CH3), 23.6 (s, –CH2–), 22.8 (s,iPr–CH3). 31P{ H} NMR
129.7 (s, Ar–CH), 124.7 (s, quat), 121.8 (s, quat), 106.4 (s, C–),
50.9 (s, NCH2CH2N–), 30.5 (s, –CH2–), 25.6 (s, –CH2–), 22.7 (s,
–CH2–), 21.8 (s, –CH2–), 21.1 (s, –CH3), 18.1 (s, –CH3).
(CDCl3, 25 ◦C): d 64.9 (s)
Preparation of 22. The general procedure was followed with
(SIMes)AuCl (0.20 g, 0.37 mmol), 1-hexyne (43 mL, 0.37 mmol),
NaOH (0.030 g, 0.75 mmol), CH2Cl2 (5 mL), and MeOH (10 mL).
The title compound was purified by column chromatography
(THF/hexane gradient 10 : 90–60 : 40) to afford 0.21 g (97.1%)
of a white powder. Anal. Calcd for C27H35AuN2: C, 55.48; H, 6.04.
Found: C, 55.73; H, 6.27. 1H NMR (CDCl3, 25 ◦C): d 6.92 (s, 4H,
Ar–H), 3.90 (s, 4H, –NCH2CH2N–), 2.30 (s, 12H, –CH3), 2.29 (s,
6H, –CH3), 2.20 (t, 2H, J = 7.5, –CH2–), 1.40 (m, 2H, –CH2–),
Preparation of 26. The general procedure was followed with
(SIMes)AuCl (0.20 g, 0.37 mmol), 2-(3-butynyloxy)tetrahydro-
2H-pyran (44.5 mL, 0.38 mmol), NaOH (0.030 g, 0.75 mmol),
CH2Cl2 (5 mL), and MeOH (10 mL). The title compound
was purified by column chromatography (THF/hexane gradient
10 : 90–80 : 20) to afford 0.20 g (82.3%) of a white powder. Anal.
Calcd for C30H39AuN2O2: C, 54.88; H, 5.99. Found: C, 54.69; H,
5.95. H NMR (CDCl3, 25 ◦C): d 6.92 (s, 4H, Ar–H), 4.53 (m,
1
1
1.26 (m, 2H, –CH2–), 0.79 (t, 3H, J = 7.20, –CH3). 13C{ H} NMR
1H, –CH–), 3.90 (s, 4H, –NCH2CH2N–), 3.78 (m, 1H, –CH2–),
3.70 (m, 1H, –CH2–), 3.47 (m, 1H, –CH2–), 3.38 (m, 1H, –CH2–),
2.53 (m, 2H, –CH2–), 2.30 (s, 12H, –CH3), 2.29 (s, 6H, –CH3),
1.76 (m, 1H, –CH2–), 1.62 (m, 1H, –CH2–), 1.50 (m, 2H, –CH2–),
◦
(CDCl3, 25 C): d 210.4 (s, carbene C), 138.5 (s, quat), 135.6 (s,
quat), 135.0 (s, quat), 129.7 (s, CH–), 115.3 (s, C–), 105.4 (s,
C–), 50.9 (s, –NCH2CH2N–), 32.5 (s, –CH2–), 22.4 (s, –CH2–),
21.1 (s, –CH3), 20.0 (s, –CH2–), 18.0 (s, –CH3), 13.7 (s, –CH3).
◦
1
1.44 (m, 2H, –CH2–), 13C{ H} NMR (CDCl3, 25 C): d 210.2 (s,
carbene C), 138.5 (s, quat), 135.6 (s, quat), 134.9 (s, quat), 129.7 (s,
Ar–CH), 117.3 (s, quat), 100.6 (s, C–), 98.5 (s, –CH–), 67.1 (s,
–CH2–), 62.0 (s, –CH2–), 50.9 (s, –NCH2CH2N–), 30.6 (s, –CH2–),
25.4 (s, –CH2–), 21.5 (s, –CH2–), 21.1 (s, –CH3), 19.5 (s, –CH2–),
18.0 (s, –CH3).
Preparation of 23. The general procedure was followed with
(SIMes)AuCl (0.20 g, 0.37 mmol), ethynyl toluene (47.0 mL,
0.371 mmol), NaOH (0.030 g, 0.75 mmol), CH2Cl2 (5 mL), and
MeOH (10 mL). The title compound was purified by column
chromatography (THF/hexane gradient 10 : 90–80 : 20) to afford
0.16 g (69.7%) of a white powder. Anal. Calcd for C30H33AuN2: C,
58.25; H, 5.38. Found: C, 58.48; H, 5.72. 1H NMR (CDCl3, 25 ◦C):
d 7.20 (AA¢BB¢, 2H, Ar–H), 6.94 (s, 4H, Ar–H), 6.91 (AA¢BB¢,
2H, Ar–H), 3.93 (s, 4H, –NCH2CH2N–), 2.33 (s, 12H, –CH3), 2.30
Preparation of 27. The general procedure was followed with
(SIMes)AuCl (0.20 g, 0.37 mmol), methyl propiolate (33.0 mL,
0.37 mmol), NaOH (0.030 g, 0.75 mmol), CH2Cl2 (5 mL), and
MeOH (10 mL). The title compound was purified by column chro-
matography (THF/hexane gradient 10 : 90–80 : 20) to afford 0.15
g (68.9%) of a white powder. Anal. Calcd for C25H29AuN2O2: C,
51.20; H, 4.98. Found: C, 50.91; H, 4.75. 1H NMR (CDCl3, 25 ◦C):
d 6.94 (s, 4H, Ar–H), 3.96 (s, 4H, –NCH2CH2N–), 3.59 (s, 3H, –
◦
1
(s, 6H, –CH3), 2.23 (s, 3H, –CH3). 13C{ H} NMR (CDCl3, 25 C):
d 210.1 (s, carbene C), 138.6 (s, quat), 135.7 (s, quat), 135.6 (s,
quat), 134.9 (s, quat), 132.1 (s, Ar–CH), 129.8 (s, Ar–CH), 128.4
(s, Ar–CH), 127.7 (s, quat or C–), 122.5 (s, quat or C–), 104.3
(s, C–), 50.9 (s, –NCH2CH2N–), 21.3 (s, –CH3), 21.1 (s, –CH3),
18.1 (s, –CH3).
1
OCH3), 2.30 (s, 6H, –CH3), 2.29 (s, 12H, –CH3). 13C{ H} NMR
(CDCl3, 25 ◦C): d 209.0 (s, carbene C), 153.9 (s, C O), 138.9
(s, quat), 135.5 (s, quat), 134.5 (s, quat), 133.3 (s, quat), 129.8 (s,
Ar–CH), 93.5 (s, C–), 51.8 (s, –OCH3), 51.0 (s, –NCH2CH2N–),
21.1 (s, –CH3), 18.0 (s, –CH3).
Preparation of 24. The general procedure was followed with
(SIMes)AuCl (0.20 g, 0.37 mmol), ethynylferrocene (0.078 g,
0.37 mmol), NaOH (0.030 g, 0.75 mmol), CH2Cl2 (5 mL), and
MeOH (10 mL). Recrystallization by diffusion of pentane into a
saturated benzene/CH2Cl2 solution afforded 0.22 g (83.2%) of the
title compound as orange needles. Anal. Calcd for C33H35AuFeN2:
Preparation of 28. The general procedure was followed with
(SIMes)AuCl (0.20 g, 0.37 mmol), ethisterone (0.12 g, 0.38 mmol;
dissolved in 10 mL methanol), NaOH (0.030 g, 0.75 mmol),
CH2Cl2 (5 mL), and MeOH (10 mL). Recrystallization by diffusion
of pentane into a saturated benzene solution afforded 0.25 g
(82.7%) of the title compound as white needles. Anal. Calcd for
1
C, 55.63; H, 4.95. Found: C, 55.99; H, 4.43. H NMR (CDCl3,
25 ◦C): d 6.94 (s, 4H, Ar–CH), 4.20 (m, 2H, CH), 4.09 (s, 5H,
CH), 3.97 (m, 2H, CH), 3.91 (s, 4H, –NCH2CH2N–), 2.3◦3 (s,
1
12H, –CH3), 2.30 (s, 6H, –CH3). 13C{ H} NMR (CDCl3, 25 C):
1
C42H53AuN2O2: C, 61.91; H, 6.56. Found: C, 62.03; H, 6.27. H
d 210.1 (s, carbene C), 138.5 (s, quat), 135.6 (s, quat), 135.0 (s,
quat), 129.7 (s, Ar–CH), 125.0 (s, C–), 101.4 (s, C–), 71.6
(s, CH), 69.7 (s, CH), 68.9 (s, quat), 67.2 (s, CH), 50.9 (s,
–NCH2CH2N–), 21.1 (s, –CH3), 18.1 (s, –CH3).
NMR (CDCl3, 25 ◦C): d 6.93 (s, 2H, Ar–H), 6.92 (s, 2H, Ar–H),
5.73 (s, 1H, CH), 3.91(s, 4H, –NCH2CH2N–), 2.47–2.20 (m,
4H, –CH2–), 2.31 (s, 12H, –CH3), 2.28 (s, 6H, –CH3), 2.13 (m, 1H,
–CH2–), 2.05 (m, 1H, –CH2–), 1.89 (m, 1H, –CH2–), 1.78–1.67 (m,
3H, –CH2–), 1.62–1.53 (m, 2H, –CH2–), 1.47–1.41 (m, 3H, –CH2–
and –CH–), 1.34 (m, 1H, –CH2–), 1.17 (m, 1H, –CH2–), 1.17 (s,
3H, –CH3), 0.97 (m, 1H, –CH2–), 0.88 (m, 1H, –CH–), 0.77 (s,
Preparation of 25. The general procedure was followed with
(SIMes)AuCl (0.20 g, 0.37 mmol), 1-ethynylcyclohexene (44.5 mL,
0.38 mmol), NaOH (0.030 g, 0.75 mmol), CH2Cl2 (5 mL), and
MeOH (10 mL). The title compound was purified by column
chromatography (THF/hexane gradient 10 : 90–80 : 20) to afford
0.21 g (93.0%) of a white powder. Anal. Calcd for C29H35AuN2:
◦
1
3H, –CH3). 13C{ H} NMR (CDCl3, 25 C): d 210.2 (s, carbene C),
199.7 (s, quat), 172.1 (s, quat), 138.5 (s, quat), 135.6 (s, quat), 134.9
(s, quat), 129.61 (s, Ar–CH), 129.58 (s, Ar–CH), 123.6 (s, CH),
122.3 (s, C–), 107.5 (s, C–), 80.1 (s, quat), 53.4 (s, –CH–), 50.9
(s, –NCH2CH2N–), 49.2 (s, –CH–), 46.4 (s, quat), 39.6 (s, –CH2–),
38.7 (s, quat), 36.3 (s, –CH–), 35.8 (s, –CH2–), 34.1 (s, –CH2–), 33.0
(s, –CH2–), 32.5 (s, –CH2–), 31.5 (s, –CH2–), 23.1 (s, –CH2–), 21.1
(s, –CH3), 20.9 (s, –CH2–), 18.1 (s, –CH3), 17.4 (s, –CH3), 12.9 (s,
–CH3).
1
C, 57.23; H, 5.80. Found: C, 57.07; H, 5.62. H NMR (CDCl3,
25 ◦C): d 6.91 (s, 4H, Ar–H), 5.87 (m, 1H, CH), 3.90 (s, 4H,
–NCH2CH2N–), 2.30 (s, 12H, –CH3), 2.28 (s, 6H, –CH3), 2.02 (m,
2H, –CH2–), 1.96 (m, 2H, –CH2–), 1.49 (m, 2H, –CH2–), 1.45 (m,
◦
1
2H, –CH2–). 13C{ H} NMR (CDCl3, 25 C): d 210.3 (s, carbene
C), 138.5 (s, quat), 135.6 (s, quat), 134.9 (s, quat), 132.0 (s, CH),
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Dalton Trans., 2011, 40, 12595–12606 | 12603
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Preparation of 29. The general procedure was followed with
(SIMes)AuCl (0.20 g, 0.37 mmol), 1-ethynyl-1-cyclohexanol
(0.046 g, 0.37 mmol), NaOH (0.030 g, 0.75 mmol), CH2Cl2 (5 mL),
and MeOH (10 mL). Recrystallization by diffusion of pentane
into a saturated benzene solution afforded 0.18 g (77.4%) of the
title compound as a white powder. Anal. Calcd for C29H37AuN2O:
–C6H5), 131.8 (d, J = 2.3, –C6H5), 129.4 (d, J = 11.3, –C6H5), 129.2
(d, J = 52.2, –C6H5), 57.8 (d, J = 3.3, –OCH◦2CH3), 17.0 (d, J =
1
6.6, –OCH2CH3). 31P{ H} NMR (CDCl3, 25 C): d 110.3 (d, J =
521.4 Hz, P(O)(OEt)2), 44.6 (d, J = 522.3, PPh3).
Preparation of (JohnPhos)Au(P(O)(OEt)2). An NMR tube
was charged with 0.040 mmol of the alkynylgold complex (13–
17) along with diethylphosphite (5.15 mL, 0.040 mmol), and C6D6
(0.5 mL). The NMR tubes were sealed in air and immersed
in an oil bath at 64 ◦C. The reactions were monitored by
NMR spectroscopy until the starting alkynylgold complex was
consumed (>95%). After the alkynylgold complex was consumed,
an internal standard (anisole or hexamethylbenzene) was added
to the reaction mixture. Comparison of the resonances for the
internal standard with the title compound provided the NMR
conversions. The reaction mixture was concentrated under vac-
uum, triturated with hexane, and dried under vacuum to afford
the gold phosphonate as a white solid. Unless specified, the NMR
and isolated yields obtained for each alkynylgold precursor are
listed in Tables 3 and 5. Anal. Calcd for C24H37AuO3P2: C, 45.58;
H, 5.90. Found: C, 45.20; H, 6.12. 1H NMR (CDCl3, 25 ◦C): d 7.85
(m, 1H, Ar–H), 7.57 (m, 2H, Ar–H), 7.49 (m, 3H, Ar–H), 7.26 (m,
1H, Ar–H), 7.18 (m, 2H, Ar–H), 3.84 (m, 4H, –OCH2CH3), 1.41
(d, 18H, J = 15.0, PC(CH3)3), 1.25 (t, 6H, J = 7.2, –OCH2CH3).
1
C, 55.59; H, 5.95. Found: C, 55.50; H, 5.79. H NMR (CDCl3,
25 ◦C): d 6.94 (s, 4H, Ar–CH), 3.90 (s, 4H, –NCH2CH2N–), 2.31
(br s, 18H, –CH3), 1.78 (s, 1H, –OH), 1.71 (m, 2H, –CH2), 1.51 (m,
◦
1
6H, –CH2), 1.27 (m, 2H, –CH2–). 13C{ H} NMR (CDCl3, 25 C):
d 210.2 (s, carbene C), 138.5 (s, quat), 135.6 (s, quat), 134.9 (s,
quat), 129.7 (s, Ar–CH), 119.4 (s, C–), 108.6 (s, C–), 68.4 (s,
quat), 50.9 (s, –NCH2CH2N–), 40.7 (s, –CH2–), 25.5 (s, –CH2–),
23.0 (s, –CH2–), 21.1 (s, –CH3), 18.1 (s, –CH3).
Preparation of 30. The general procedure was followed with
(SIMes)AuCl (0.20 g, 0.37 mmol), 2-methyl-3-butyn-2-ol (36 mL,
0.37 mmol), NaOH (0.030 g, 0.75 mmol), CH2Cl2 (5 mL), and
MeOH (10 mL). Recrystallization by diffusion of pentane into
a saturated benzene solution afforded 0.16 g (73.5%) of the title
compound as a white powder. Anal. Calcd for C26H33AuN2O: C,
53.24; H, 5.67. Found: C, 53.20; H, 5.29. 1H NMR (CDCl3, 25 ◦C):
d 6.94 (s, 4H, Ar–H), 3.90 (s, 4H, –NCH2CH2N–), 2◦.30 (s, 18H,
1
–CH3), 1.41 (s, 6H, –CH3). 13C{ H} NMR (CDCl3, 25 C): d 210.0
◦
1
13C{ H} NMR (CDCl3, 25 C): d 150.2 (d, J = 16.1, quat), 141.2
(d, J = 6.8, quat), 134.7 (d, J = 6.8,Ar–CH), 132.9 (d, J = 7.4,
Ar–CH), 130.6 (d, J = 1.8, Ar–CH), 129.5 (s, Ar–CH), 128.8 (s,
Ar–CH), 128.6 (s, Ar–CH), 126.8 (dd, J = 34.8, 6.2, quat), 126.8
(dd, J = 5.3, 1.4, Ar–CH), 56.9 (d, J = 2.3, –OCH2CH3), 37.8 (d,
18.5, PC(CH3)3)), 31.0 (dd, J = 6.8, 1.1, PC(CH3)3), 16.9 (d, J =
(s, carbene C), 138.5 (s, quat), 135.6 (s, quat), 134.9 (s, quat), 129.7
(s, Ar–CH), 118.0 (s, C–), 109.1 (s, C–), 65.5 (s, quat), 50.9 (s,
–NCH2CH2N–), 32.6 (s, –CH3), 21.1 (s, –CH3), 18.1 (s, –CH3).
Preparation of 31. The general procedure was followed with
(SIMes)AuCl (0.20 g, 0.37 mmol), propargyl alcohol (22 mL, 0.38
mmol), NaOH (0.030 g, 0.75 mmol), CH2Cl2 (5 mL), and MeOH
(10 mL). Recrystallization by diffusion of pentane into a saturated
benzene/CH2Cl2 solution of the title compound afforded 0.12 g
(57.9%) white needles. Anal. Calcd for C24H29AuN2O: C, ◦51.62;
◦
6.6, –OCH2CH3). 31P{ H} NMR (CDCl3, 25 C): d 111.4 (d, J =
1
473.2, –P(O)(OEt)2), 65.6 (d, J = 473.0, PtBu2).
Preparation of (tBuXPhos)Au(P(O)(OEt)2). An NMR tube
was charged with 0.040 mmol of the alkynylgold complex (18–
21) along with diethylphosphite (5.15 mL, 0.040 mmol), and C6D6
(0.5 mL). The NMR tubes were sealed in air and immersed
in an oil bath at 64 ◦C. The reactions were monitored by
NMR spectroscopy until the starting alkynylgold complex was
consumed (>95%). After the alkynylgold complex was consumed,
an internal standard (anisole or hexamethylbenzene) was added
to the reaction mixture. Comparison of the resonances for the
internal standard with the title compound provided the NMR
conversions. The reaction mixture was concentrated under vac-
uum, triturated with hexane, and dried under vacuum to afford
the gold phosphonate as a white solid. Unless specified, the NMR
and isolated yields obtained for each alkynylgold precursor are
listed in Tables 3 and 5. Anal. Calcd for C33H55AuO3P2: C,◦52.24;
1
H, 5.23. Found: C, 51.85; H, 5.85. H NMR (CDCl3, 25 C): d
6.93 (s, 4H, Ar–H), 4.24 (d, 2H, J = 6.6, –CH2–), 3.93 (s, 4H,
–NCH2CH2N–), 2.31 (s, 12H, –CH3), 2.29 (s, 6H, –CH3), 1.32
(t, 1H, J = 6.0, –OH). 13C{ H} NMR (CDCl3, 25 ◦C): d 209.8
1
(carbene C), 138.7 (s, quat), 135.5 (s, quat), 134.7 (s, quat), 129.6
(s, Ar–CH), 123.0 (s, C–), 102.6 (s, C–), 52.1 (s, –OCH2–),
50.9 (s, –NCH2CH2N–), 21.1 (s, –CH3), 18.0 (s, –CH3).
Preparation of Ph3PAu(P(O)(OEt)2). An NMR tube was
charged with 0.040 mmol of the alkynylgold complex (1–12) along
with diethylphosphite (5.15 mL, 0.040 mmol), and C6D6 (0.5 mL).
The NMR tubes were sealed in air and immersed in an oil bath at
64 ◦C. The reactions were monitored by NMR spectroscopy until
the starting alkynylgold complex was consumed (>95%). After
the alkynylgold complex was consumed, an internal standard
(anisole or hexamethylbenzene) was added to the reaction mixture.
Comparison of the resonances for the internal standard with the
title compound provided the NMR conversions. The reaction
mixture was concentrated under vacuum, triturated with a 2 : 1
mixture of diethylether : hexane, and dried under vacuum to afford
the gold phosphonate as a white solid. Unless specified, the
isolated yields obtained for each alkynylgold precursor are listed
in Tables 2 and 5. Anal. Calcd for C22H25AuO3P: C, 44.31; H,
4.23. Found: C, 44.21; H, 4.27. 1H NMR (CDCl3, 25 ◦C): d 7.55–
7.46 (m, 15H, –C6H5), 4.09 (m, 4H, –OCH2CH3), 1.34 (t, 6H, J =
1
H, 7.31. Found: C, 52.01; H, 7.45. H NMR (CDCl3, 25 C): d
7.87 (m, 1H, Ar–H), 7.46 (m, 2H, Ar–H), 7.26 (m, 1H, Ar–H),
7.17 (m, 2H, Ar–H), 3.77 (m, 4H, –CH2–), 3.04 (sept, 1H, J = 6.9,
i
iPrCH), 2.36 (sept, 2H, J = 6.6, PrCH), 1.43 (d, 18H, J = 14.4,
i
PC(CH3)3), 1.35 (d, 6H, J = 6.6, Pr–CH3), 1.32 (d, 6H, J = 6.6,
iPr–CH3), 1.20 (t, 6H, J = 7.2, –CH2CH3), 0.91 (d, 6H, J = 6.0,
◦
1
iPr–CH3). 13C{ H} NMR (CDCl3, 25 C): d 149.1 (s, quat), 148.3
(d, J = 16.9, quat), 145.4 (s, quat), 135.6 (d, J = 6.6, Ar–CH), 135.2
(d, J = 5.0, quat), 134.7 (d, J = 8.4, Ar–CH), 130.1 (d, J = 2.3,
Ar–CH), 129.1 (dd, J = 32.2, 6.4, quat), 126.4 (dd, J = 3.9, 1.7,
Ar–CH), 122.4 (s, Ar–CH), 56.6 (d, J = 2.3, –OCH2CH3), 38.4 (d,
J = 19.0, quat), 33.4 (s, iPrCH), 31.4 (d, J = 6.6, PC(CH3)3), 31.0
◦
1
7.2, –CH3). 13C{ H} NMR (CDCl3, 25 C): d 134.2 (d, J = 14.0,
12604 | Dalton Trans., 2011, 40, 12595–12606
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(s, iPrCH), 26.4 (s, iPr–CH3), 23.6 (s, iPr–CH3), 23.0 (s, iPr–CH3),
quat), 134.2 (s, quat), 129.8 (s, Ar–CH), 71.8 (d, J = 1.7, –OCH2–),
51.2 (d, J = 5.6, –NCH2–), 31.8 (d, J = 5.3, quat), 22.7 (s, –CH3),
◦
1
16.8 (d, J = 7.2, –OCH2CH3). 31P{ H} NMR (CDCl3, 25 C): d
112.7 (d, J = 479.3, P(O)(OEt)2), 65.5 (d, J = 479.0, PtBu2).
21.04 (s, –CH3), 21.00 (s, –CH3), 18.0 (s, –CH3). 31P{ H} NMR
1
(CDCl3, 25 ◦C): d 110.9 (s).
Preparation of (SIMes)Au(P(O)(OEt)2). An NMR tube was
charged with 0.040 mmol of the alkynylgold complex (22–31)
diethylphosphite (5.15 mL, 0.040 mmol), and C6D6 (0.5 mL).
The NMR tubes were sealed in air and immersed in an oil bath
at 64 ◦C. The reactions were monitored by NMR spectroscopy
until the starting alkynylgold complex was consumed (>95%).
As the title compound is insoluble in C6D6, it was separated
from the reaction mixture by centrifugation and triturated with
fresh benzene (0.5 mL) to afford a white solid (dried under
vacuum). Unless specified, the isolated yields obtained for each
alkynylgold precursor are listed in Tables 4 and 5. Anal. Calcd for
C25H36AuN2O3P: C, 46.88; H, 5.67. Found: C, 46.63; H, 5.86. 1H
NMR (CDCl3, 25 ◦C): d 6.94 (s, 4H, Ar–H), 4.00 (s, 4H, –NCH2–),
3.55 (m, 4H, –OCH2–), 2.32 (s, 12H, Ar–CH3), 2.29 (s, 6H, Ar–
Acknowledgements
The authors thank the National Science Foundation for the funds
to purchase the NMR spectrometer (CHE-0521108), the Camille
and the Camille and Henry Dreyfus Foundation (SU-00-020) for
a New Faculty Award, and Bucknell University for a Scholarly
Development Grant (RASJ). The authors thank Professor David
Rovnyak for helpful discussions.
References
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1
CH3), 0.99 (t, 6H, J = 7.0, –CH2CH3). 13C{ H} NMR (CDCl3,
25 ◦C): d 216.2 (d, J = 170.0, carbene C), 139.0 (s, quat), 135.6 (s,
quat), 134.3 (s, quat), 129.7 (s, Ar–CH), 57.2 (s, –NCH2–), 51.1 (d,
J = 6.2, OCH2CH3), 21.0 (s, Ar–CH3), 18.0 (s, Ar–CH3), 16.7 (d,
5 E. Jimenez-Nunez and A. M. Echavarren, Chem. Rev., 2008, 108, 3326.
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48, 9346.
◦
1
J = 6.6, OCH2CH3). 31P{ H} NMR (CDCl3, 25 C): d 112.2 (s).
Preparation of (JohnPhos)Au(P(O)(O2C2Me4)). An NMR
tube was charged with 0.040 mmol of 13 along with
HP(O)(O2C2Me4) (0.0066 g, 0.040 mmol), and C6D6 (0.5 mL). The
NMR tube was sealed in air and immersed in an oil bath at 64 ◦C.
After 14 h, the reaction mixture was concentrated under vacuum,
triturated with hexane, and dried under vacuum. Purification
of residue by column chromatography (Silica gel : THF/MeOH
gradient 100 : 0–50 : 50) afforded the gold phosphonate as a viscous
oil (0.022 g, 84%). Anal. Calcd for C26H39AuO3P2: C, 47.42; H,
5.97. Found: C, 47.08; H, 6.51. 1H NMR (CDCl3, 25 ◦C): d 7.85
(m, 1H, Ar–H), 7.57 (m, 3H, Ar–H), 7.49 (m, 2H, Ar–H), 7.27 (m,
1H, Ar–H), 7.16 (m, 2H, Ar–H), 1.40 (d, 18H, J = 15.6, C(CH3)3),
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1
1.37 (s, 6H, –CH3), 1.20 (s, 6H, –CH3). 13C{ H} NMR (CDCl3,
25 ◦C): d 150.2 (d, J = 16.0, quat), 141.0 (d, J = 6.5, quat), 134.5(d,
J = 6.8, Ar–CH), 132.8 (d, J = 7.4, Ar–CH), 130.5 (d, J = 2.3,
Ar–CH), 129.6 (s, Ar–CH), 129.5 (s, Ar–CH), 128.6 (s, Ar–CH),
126.7 (dd, J = 35.0, 6.5, quat), 126.8 (dd, J = 5.7, 1.5, Ar–CH),
83.5 (d, J = 4.9, –OC2Me4), 37.5 (dd, J = 18.3, 1.3, –C(CH3)3), 31.0
(dd, J = 6.8, 1.6, –C(CH3)3), 25.2 (d, J ◦= 2.9, –CH3), 25.1 (d, J =
1
5.4, –CH3). 31P{ H} NMR (CDCl3, 25 C): d 120.2 (d, J = 484.1,
-
–P(O)(O2C2Me4), 65.0 (d, J = 483.6, –P(C(CH3)3)2 ).
25 A. Christiansen, C. Li, M. Garland, D. Selent, R. Ludwig, R. Franke
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Preparation of (SIMes)Au(P(O)(OCH2CMe2CH2O-)). An
NMR tube was charged with 0.040 mmol of 29 along with
HP(O)(OCH2CMe2CH2O-) (0.0060 g, 0.040 mmol), and C6D6
(0.5 mL). The NMR tube was sealed in air and immersed in
an oil bath at 64 ◦C. After 14 h, the reaction mixture was
concentrated under vacuum, triturated with hexane, and dried
under vacuum. Purification of residue by column chromatography
(Silica gel : THF/MeOH gradient 100 : 0–50 : 50) afforded the gold
phosphonate as a white solid (0.020 g, 77%). Anal. Calcd for
C26H36AuN2O3P: C, 47.86; H, 5.56. Found: C, 47.51; H, 5.93. 1H
NMR (CDCl3, 25 ◦C): d 6.96 (s, 4H, Ar–H), 4.00 (s, 4H, –NCH2–),
3.42 (m, 4H, –OCH2–), 2.32 (s, 12H, –CH3), 2.29 (s, 6H, –CH3),
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1
1.03 (s, 3H, –CH3), 0.58 (s, 3H, –CH3). 13C{ H} NMR (CDCl3,
25 ◦C): d 215.8 (d, J = 170.3, carbene C), 139.0 (s, quat), 135.0 (s,
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12606 | Dalton Trans., 2011, 40, 12595–12606
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