Synthesis of axially chiral gold complexes and their applications in asymmetric catalyses

Article abstract of DOI:10.3762/bjoc.9.261

Several novel chiral N-heterocyclic carbene and phosphine ligands were prepared from (S)-BINOL. Moreover, their ligated Au complexes were also successfully synthesized and characterized by X-ray crystal diffraction. A weak gold-π interaction between the Au atom and the aromatic ring in these gold complexes was identified. Furthermore, we confirmed the formation of a pair of diastereomeric isomers in NHC gold complexes bearing an axially chiral binaphthyl moiety derived from the hindered rotation around C-C and C-N bonds. In the asymmetric intramolecular hydroamination reaction most of these chiral Au(I) complexes showed good catalytic activities towards olefins tethered with a NHTs functional group to give the corresponding product in moderate yields and up to 29% ee.

Full text of DOI:10.3762/bjoc.9.261

Synthesis of axially chiral gold complexes and their
applications in asymmetric catalyses
Yin-wei Sun1, Qin Xu*1 and Min Shi*1,2
Full Research Paper
Open Access
Address:
Beilstein J. Org. Chem. 2013, 9, 2224–2232.
1Key Laboratory for Advanced Materials and Institute of Fine
Chemicals, School of Chemistry & Molecular Engineering, East China
University of Science and Technology, and 130 MeiLong Road,
Shanghai 200237, People’s Republic of China, and 2State Key
Laboratory of Organometallic Chemistry, Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin
Road, Shanghai 200032, People’s Republic of China
doi:10.3762/bjoc.9.261
Received: 02 July 2013
Accepted: 27 September 2013
Published: 28 October 2013
This article is part of the Thematic Series "Gold catalysis for organic
synthesis II".
Email:
Qin Xu* - qinxu@ecust.edu.cn; Min Shi* - Mshi@mail.sioc.ac.cn
Guest Editor: F. D. Toste
* Corresponding author
© 2013 Sun et al; licensee Beilstein-Institut.
License and terms: see end of document.
Keywords:
asymmetric gold catalysis; chiral Au catalysts; gold-π interaction;
NHC gold complex
Abstract
Several novel chiral N-heterocyclic carbene and phosphine ligands were prepared from (S)-BINOL. Moreover, their ligated Au
complexes were also successfully synthesized and characterized by X-ray crystal diffraction. A weak gold-π interaction between the
Au atom and the aromatic ring in these gold complexes was identified. Furthermore, we confirmed the formation of a pair of
diastereomeric isomers in NHC gold complexes bearing an axially chiral binaphthyl moiety derived from the hindered rotation
around C–C and C–N bonds. In the asymmetric intramolecular hydroamination reaction most of these chiral Au(I) complexes
showed good catalytic activities towards olefins tethered with a NHTs functional group to give the corresponding product in
moderate yields and up to 29% ee.
Introduction
After the long-held assumption of the non-reactivity of gold uncommon. Very few efficient chiral NHC–gold catalysts
complexes, numerous reactions catalyzed by gold complexes have been known up to the year of 2013. So far, several axially
have emerged in the last 2 decades [1-9]. In the past few years, chiral NHC–gold catalysts based on binaphthyl skeleton such
reports on gold-catalyzed organic transformations have as 1 and 2 [46,49] have been reported with good to excellent
increased substantially [10-29]. Homogeneous gold catalysis chiral inductions in asymmetric gold catalysis (Figure 1).
has proven to be a powerful tool in organic synthesis. However, Encouraged by these results, we attempted to develop novel
chiral gold complexes [30-45], especially chiral NHC–gold types of axially chiral NHC–gold catalysts based on the bi-
complex-catalyzed asymmetric reactions [46-53] are still naphthyl skeleton.
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Figure 1: Monodentate chiral NHC gold catalysts in recent years.
Very recently, Echavarren’s group has reported a very impor- Tf2O and pyridine in DCM in 99% yield. The usage of
tant gold–arene interaction in dialkylbiarylphosphane gold dimethylbis(diphenylphosphino)xanthene (XantPhos) as a
complexes, which is very useful in gold catalysis [54]. It has ligand and Pd2(dba)3 as a catalyst in the presence of Cs2CO3,
been disclosed that there was a weak gold-π interaction between facilitated the reaction of (S)-7 with benzylamine in toluene to
the gold atom and the aromatic ring in catalysts 1 [46]. On the give the desired compound (S)-8 in 57% yield [49]. Reduction
basis of this finding, we envisaged that if an aryl group is intro- of (S)-8 by using Pd/C and H2 in MeOH produced the desired
duced near the ligated gold atom, the gold–arene interaction compound (S)-9 in 95% yield.
may affect the catalytic efficiency in gold catalysis (Figure 1).
The preparation of chiral benzimidazolium salt (S)-13 is shown
Results and Discussion
in Scheme 2. Based on our previous work [52], the coupling
Synthesis of the carbene–Au(I) complexes. The synthesis of reaction between compound (S)-9 and 1-bromo-2-nitrobenzene
compound 9 was reported by Slaughter and co-workers was carried out by using Pd2(dba)3 as the catalyst in the pres-
(Scheme 1) [49]. The usage of (S)-BINOL as the starting ma- ence of bis[2-(diphenylphosphino)phenyl] ether (DPEphos) and
terial to react with trifluoromethanesulfonic anhydride in the Cs2CO3, affording the desired compound (S)-10 in 94% yield
presence of DIPEA afforded at 0 °C in dichloromethane the [51]. Reduction of (S)-10 was performed under H2 (1.0 atm)
corresponding product (S)-2'-hydroxy-1,1'-binaphthyl-2-yl atmosphere by using Pd/C as a catalyst, giving the desired com-
trifluoromethanesulfonate (5) in good yield. The crude product pound (S)-11 in 95% yield. The subsequent cyclization of (S)-
and NiCl2(dppe) (10 mol %) was dissolved in toluene under 11 with triethyl orthoformate was carried out at 100 °C in the
argon. To this solution was added dropwise a 1.0 M THF solu- presence of p-toluenesulfonic acid, affording the desired prod-
tion of 3,5-bis(trifluoromethyl)phenylmagnesium bromide, uct (S)-12 in 89% yield. The corresponding benzimidazolium
which afforded (S)-6 in 33% yield in two steps under reflux salt (S)-13 was obtained in quantitative yield upon treating the
[55]. Then, (S)-7 was obtained by treatment of (S)-6 with benzimidazole ring of (S)-12 with methyl iodide in acetonitrile
Scheme 1: Synthesis of compound 9.
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Beilstein J. Org. Chem. 2013, 9, 2224–2232.
Scheme 2: Synthesis of N-heterocyclic carbene precursor.
under reflux (Scheme 2). Moreover, treatment of the benzimid- and the Au atom in (S)-15a was only 3.7 Å (Figure 2).
azole ring of (S)-12 by using benzyl bromide upon heating in The distance from the Au atom to the center of the bis(trifluo-
dioxane could produce the corresponding benzimidazolium salt romethyl)phenyl ring (C29–C34) in (S)-15b was 3.5 Å
(S)-14 also in quantitative yield (Scheme 3).
(Figure 3). Thus, their X-ray crystal structures clearly revealed
the presence of a weak gold–π interaction between the Au atom
With these NHC precursor salts (S)-13 and (S)-14 in hand, their and the aromatic rings in these gold complexes. Because of the
coordination pattern with Au was examined. Benzimidazolium gold–π interaction, the C–N bond could not rotate freely, giving
salts (S)-13 and (S)-14 were treated with AuCl·S(Me)2 in aceto- two diastereomeric rotamers (S)-15a and (S)-15b. Slaughter and
nitrile in the presence of NaOAc under reflux, giving the corres- co-workers have also found two rotamers in gold complexes 1
ponding Au complexes (S)-15 [two diastereomers: (S)-15a in caused by the handicap of C–N bond rotation on the basis of
46% yield and (S)-15b in 37% yield] and (S)-16 in 75% total X-ray diffraction and named them as “out” rotamer and “in”
yield [the two diastereomers: (S)-16a and (S)-16b can not be rotamer [49] (Scheme 5). Their energy barrier has been also
separated by silica gel column chromatography] as a white solid disclosed by DFT calculations.
after purification with silica gel column chromatography
(Scheme 4). The ratio of (S)-16a and (S)-16b was identified as Synthesis of the P–Au(I) complexes. The synthesis of the Au
1:2 on the basis of 1H NMR spectroscopic data. After recrystal- complexes (S)-18 and (S)-22 is shown in Scheme 6. Com-
lization from the mixed solvent of DCM and pentane, the single pounds (S)-17 and (S)-19 were prepared according to published
crystals of diastereomers (S)-15a and (S)-15b were obtained and literature procedures [56]. Compound (S)-17 was treated with
their structures were confirmed by the X-ray crystal structure AuCl·S(Me)2 in acetonitrile at room temperature to give the
diffraction (Figure 2 and Figure 3). The distance between the corresponding Au complex (S)-18 in 88% yield as a white solid
center of the aromatic ring in one naphthyl moiety (C20–C25) after purification with silica gel column chromatography. The
Scheme 3: Synthesis of benzimidazolium salt (S)-14.
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Beilstein J. Org. Chem. 2013, 9, 2224–2232.
Scheme 4: Synthesis of carbene Au complexes.
Figure 2: The crystal data of gold complex (S)-15a was deposited in
the CCDC with the number 883917. Empirical formula:
C36H22AuF6IN2; formula weight: 920.42; crystal color, colorless;
crystal dimensions: 0.321 × 0.212 × 0.143 mm; crystal system:
orthorhombic; lattice parameters: a = 9.6909(5) Å, b = 18.5814(9) Å,
c = 36.0427(18) Å, α = 90o, β = 90o, γ = 90o, V = 6490.2(6) Å3; space
group: P2(1)2(1)2(1); Z = 8; Dcalc = 1.884 g/cm3; F000 = 3504; final R
indices [I > 2sigma(I)]: R1 = 0.0421; wR2 = 0.0793.
Figure 3: The crystal data of gold complex (S)-15b was deposited in
the CCDC with the number 883916. Empirical formula:
C36H22AuF6IN2; formula weight: 920.42; crystal color, colorless;
crystal dimensions: 0.265 × 0.211 × 0.147 mm; crystal system:
orthorhombic; lattice parameters: a = 7.6103(5) Å, b = 12.6408(8) Å,
c = 34.029(2) Å, α = 90o, β = 90o, γ = 90o, V = 3273.6(4) Å3; space
group: P2(1)2(1)2(1); Z = 4; Dcalc = 1.868 g/cm3; F000 = 1752; final R
indices [I > 2sigma(I)]: R1 = 0.0482; wR2 = 0.1072.
structure of (S)-18 was confirmed by the X-ray crystal structure
diffraction (Figure 4). The distance from the Au atom to the
center of the aromatic ring (C11, C12 and C17–C20) in one
naphthyl moiety was 3.3 Å.
Then, the obtained compound (S)-20 was treated with SiHCl3 in
the presence of triethylamine in toluene at 120 °C, giving (S)-
The compound (S)-19 and NiCl2(dppe) (10 mol %) were diphenyl(2'-phenyl-1,1'-binaphthyl-2-yl)phosphine (21) in 81%
dissolved in toluene under argon. To this solution was added yield. The corresponding gold complex (S)-22 was obtained in
dropwise a 1.0 M THF solution of phenylmagnesium bromide 91% yield upon treating (S)-21 with the same method as the
and the desired compound (S)-20 was afforded in 21% yield. gold complex (S)-18. The structure of (S)-22 was confirmed by
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Beilstein J. Org. Chem. 2013, 9, 2224–2232.
Scheme 5: Rotamers of 1a and 1b by DFT calculation reported by
Slaughter’s group.
Figure 4: The crystal data of gold complex (S)-18 was deposited in the
CCDC with the number 920617. Empirical formula: C32H23AuClOP;
formula weight: 686.89; crystal color, colorless; crystal dimensions:
0.212 × 0.139 × 0.101 mm; crystal system: orthorhombic; lattice para-
meters: a = 9.0411(7) Å, b = 13.4833(10) Å, c = 21.9878(16) Å,
α = 90o, β = 90o, γ = 90o, V = 2680.4(3) Å3; space group:
P2(1)2(1)2(1); Z = 4; Dcalc = 1.702 g/cm3; F000 = 1336; final R indices
[I > 2sigma(I)]: R1 = 0.0378; wR2 = 0.0680.
catalysts in a variety of reactions. High enantioselectivities were
achieved in the asymmetric intramolecular hydroamination of
allenes by using a variety of chiral phosphine–Au(I) complexes
[57-63]. On the other hand, the intramolecular hydroamination
of olefins is a more important reaction in organic synthesis and
has been widely reported [64-68]. Recently, the enantioselect-
ive intramolecular hydroamination of olefins has also been
Scheme 6: The synthesis of P–Au complexes.
X-ray crystal structure diffraction (Figure 5). The crystal struc- significantly improved by using various transition metal
ture of (S)-22 (Figure 5) revealed that the distance from the Au complexes or other metal complexes [69-77]. However, to the
atom to the center of the phenyl ring (C21–C26) was 4.5 Å. best of our knowledge, the enantioselective intramolecular
During the process of the preparation of (S)-21, we found a hydroamination of olefins catalyzed by gold complexes has not
small amount of naphtho[1,2-g]chrysene (23), presumably been reported yet. We therefore applied our Au complexes to
derived from a cross coupling of compound (S)-19 with the asymmetric catalysis of the intramolecular hydroamination
PhMgBr. Its structure was also confirmed by the X-ray crystal of olefin 24 tethered with a NHTs functional group.
structure diffraction (Figure SI-1 in Supporting Information
File 1).
Treatment of olefin 24 with the axially chiral gold complex (S)-
22 and AgOTf (5 mol %) in toluene at 85 oC for 36 h afforded
The catalytic activities of these gold complexes were examined pyrrolidine derivative 25 in 46% yield and 17% ee. While using
by the gold-catalyzed asymmetric intramolecular hydroamina- AgSbF6 or AgNTf2 as additives, only trace amounts of 25 were
tion of olefin 24 tethered with a NHTs functional group.
formed. Further screening of silver salts revealed that AgOTs
showed the best catalytic activity in this reaction, giving 25 in
Intramolecular hydroamination reaction catalyzed by Au(I) 72% yield and 27% ee (Table 1, entries 1–6). The usage of
complexes. We synthesized a variety of Au complexes both other solvents such as DCE, CH3CN and THF, decreased
neutral and cationic and subsequently used these complexes as significantly the yield (Table 1, entries 7–9). The employment
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Table 1: Asymmetric intramolecular hydroamination catalyzed by Au
complexes.
entrya Au cat.
Ag salt solvent yield (%)b ee (%)c
1
2
22
22
AgOTf
toluene
46
trace
69
17
–d
AgSbF6 toluene
CF3CO toluene
OAg
3
22
11
4
5
22
22
AgOTs toluene
72
15
27
10
0
AgBF4
toluene
6
22
AgNTf2 toluene
AgOTs CH3CN
48
7
22
12
27
29
–d
24
27
7
8
22
AgOTs
AgOTs
DCE
THF
11
9
22
N.R.
58
10
11
12
13
14
18
AgOTs toluene
AgOTs toluene
AgOTs toluene
AgOTs toluene
AgOTs toluene
16
65
Figure 5: The crystal data of gold complex (S)-22 was deposited in the
CCDC with the number 928664. Empirical formula: C38H27AuClP;
formula weight: 746.98; crystal color, habit: yellow; crystal system:
monoclinic; crystal size: 0.21 × 0.19 × 0.11; lattice parameters:
a = 10.1476(9) Å, b = 15.7426(14) Å, c = 10.5615(9) Å, α = 90o,
β = 115.257(2)o, γ = 90o, V = 1525.9(2) Å3; space group: P2(1); Z = 4;
Dcalc = 1.626 g/cm3; F000 = 732; final R indices [I > 2sigma(I)]:
R1 = 0.0231; wR2 = 0.0538.
15a
15b
none
42
51
10
–d
N.R.
aThe reaction was carried out on a 0.1 mmol scale in solvents
(1.0 mL). bIsolated yield. cMeasured by chira HPLC. dNot determined.
fied by a silica gel flash column chromatography to afford gold-
of other axially chiral Au complexes in this reaction led to complexes (S)-15a (84 mg) in 46% yield and (S)-15b (68 mg)
similar results, affording 25 in 42–65% yields and 7–2–7% ee in 37% yield. A single crystal grown from complex (S)-15a or
(Table 1, entries 10–13). The control experiment indicated that (S)-15b in a saturated solution of CH2Cl2/pentane was suitable
no reaction occurred in the absence of a Au catalyst (Table 1, for X-ray crystal analysis. (S)-15a: white solid; [α]D20 −64.7 (c
entry 14).
0.10, CH2Cl2); 1H NMR (400 MHz, CDCl3, TMS) δ 8.17–8.13
(m, 2H, ArH), 7.94 (d, J = 8.8 Hz, 1H, ArH), 7.90–7.88 (m, 1H,
ArH), 7.74–7.70 (m, 1H, ArH), 7.66–7.59 (m, 3H, ArH),
Conclusion
Axially chiral Au(I) complexes exhibiting a binaphthalene scaf- 7.56–7.50 (m, 2H, ArH), 7.42 (d, J = 8.4 Hz, 1H, ArH),
fold with NHC or phosphine gold complexes on one side and an 7.34–7.28 (m, 4H, ArH), 7.06 (s, 2H, ArH), 6.86–6.82 (m, 1H,
arene moiety on another side were prepared starting from ArH), 5.60 (d, J = 8.4 Hz, 1H, ArH), 3.78 (s, 3H, CH3);
axially chiral BINOL. A weak gold–π interaction between the 19F NMR (376 MHz, CDCl3, CFCl3) δ −63.096; 13C NMR
Au atom and the aromatic ring in these gold complexes was (100 MHz, CDCl3) δ 141.5, 140.8, 134.9, 134.5, 133.4, 132.9,
identified. These axially chiral Au(I) complexes showed 132.6, 131.3, 131.0, 130.9, 130.7, 129.9, 129.2, 129.1, 129.0,
moderate catalytic activities along with low chiral inductions in 128.5, 128.41, 128.37, 127.9, 127.6, 127.3, 126.9, 126.8, 126.4,
the asymmetric intramolecular hydroamination reaction of 123.7, 123.4, 121.0, 120.6, 113.2, 111.4, 34.8; IR (CH2Cl2) ν:
olefin 24 tethered with a functional group of NHT.
3059, 2926, 1594, 1385, 1346, 1277, 1182, 1133, 897, 820, 745,
713 cm−1; HRMS–ESI: [M + NH4]+ calcd for C36H26AuF6IN3,
938.0736; found, 938.0728. (S)-15b: white solid; [α]D20 −66.1
(c 1.45, CH2Cl2); 1H NMR (400 MHz, CDCl3, TMS) δ 8.17 (d,
J = 8.4 Hz, 1H, ArH), 8.13 (d, J = 8.0 Hz, 1H, ArH), 7.85 (d,
J = 8.0 Hz, 1H, ArH), 7.79–7.69 (m, 4H, ArH), 7.63 (d,
J = 8.0 Hz, 1H, ArH), 7.59–7.54 (m, 3H, ArH), 7.50–7.46 (m,
1H, ArH), 7.23 (d, J = 8.8 Hz, 2H, ArH), 7.17 (s, 2H, ArH),
7.08–7.04 (m, 1H, ArH), 6.47–6.42 (m, 2H, ArH), 3.94 (s, 3H,
Experimental
Synthesis of NHC–Au(I) complexes (S)-15a
and (S)-15b
The compound (S)-13 (145 mg, 0.2 mmol) and AuCl·S(Me)2
(59 mg, 0.2 mmol), NaOAc (33 mg, 0.4 mmol) were heated
under reflux in CH3CN (2 mL) overnight. The volatiles were
then removed under reduced pressure and the residue was puri-
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Beilstein J. Org. Chem. 2013, 9, 2224–2232.
CH3); 19F NMR (376 MHz, CDCl3, CFCl3) δ −62.451; 124.1, 123.4; IR (CH2Cl2) ν: 3054, 1589, 1494, 1480, 1436,
13C NMR (100 MHz, CDCl3) δ 134.6, 134.5, 134.1, 134.0, 1306, 1265, 1098, 1027, 819, 763, 744, 698 cm−1; HRMS–ESI:
133.6, 131.4, 131.34, 131.27, 129.1, 129.0, 128.8, 128.7, [M + NH4]+ calcd for C38H31AuClNP, 764.1543; found,
128.66, 128.58, 128.5, 128.3, 128.2, 127.8, 126.9, 126.5, 124.1, 764.1532.
123.4, 118.6, 31.9; IR (CH2Cl2) ν: 2923, 2851, 1726, 1465,
General procedure for the intramolecular
1387, 1277, 1181, 1131, 894, 823, 743, 712, 681 cm−1;
hydroamination reaction catalyzed by Au(I)
complexes
HRMS–ESI: [M + NH4]+ calcd for C36H26AuF6IN3, 938.0736;
found, 938.0725.
In a similar way as described in reference [51], a mixture of Au
catalyst (5 mol %) and AgX (5 mol %) in solvent (0.5 mL) was
stirred at room temperature for 5 min under argon, then a solu-
tion of compound 24 (39.1 mg, 0.10 mmol) in solvent (0.5 mL)
was added into the resulting solution. The resulting suspension
was stirred at 85 °C for 36 h. Column chromatography of the
reaction mixture gave the desired product. The enantiomeric
purity of the product was determined by chiral HPLC analysis.
Compound 25: 1H NMR (400 MHz, CDCl3, TMS) δ 7.61 (d,
J = 8.0 Hz, 2H, ArH), 7.27–7.09 (m, 12H, ArH), 4.17 (d,
J = 10.4 Hz, 1H, CH2), 3.94 (dd, J1 = 10.4 Hz, J2 = 0.4 Hz, 1H,
CH2), 3.82–3.74 (m, 1H, CH), 2.78 (ddd, J1 = 12.4 Hz,
J2 = 7.2 Hz, J3 = 0.4 Hz, 1H, CH2), 2.38 (s, 3H, CH3), 2.26 (dd,
J1 = 12.4 Hz, J2 = 7.2 Hz, 1H, CH2), 1.25 (d, J = 6.4 Hz, 3H,
CH3); 13C NMR (100 MHz, CDCl3) δ 145.6, 144.8, 142.9,
135.3, 129.5, 128.43, 128.42, 127.1, 126.6, 126.42, 126.39,
126.2, 58.3, 55.4, 52.2, 45.9, 22.1, 21.4; [α]D20 20.1 (c 1.2,
CH2Cl2), for 29% ee; Chiralcel PA-2, hexane/iPrOH = 60/40,
0.5 mL/min, 214 nm, tmajor = 45.07 min, tminor = 27.49 min.
Synthesis of chiral P–Au(I) complexes (S)-18
and (S)-22
The compound (S)-17 (454 mg, 1.0 mmol) and AuCl·S(Me)2
(294 mg, 1.0 mmol) were stirred in CH3CN (10 mL) overnight.
The volatiles were then removed under reduced pressure and
the residue was purified by silica gel flash column chromatog-
raphy to afford gold-complex (S)-18 (603 mg) in 88% yield. A
single crystal grown from complex (S)-18 in a saturated solu-
tion of CH2Cl2/pentane was suitable for X-ray crystal analysis.
(S)-18: white solid; [α]D20 −35.4 (c 0.20, CH2Cl2); 1H NMR
(400 MHz, CDCl3, TMS) δ 7.99–7.93 (m, 3H, ArH), 7.80 (d,
J = 8.4 Hz, 1H, ArH), 7.60–7.56 (m, 1H, ArH), 7.50–7.45 (m,
3H, ArH), 7.42–7.17 (m, 12H, ArH), 6.86–6.82 (m, 1H, ArH),
6.45 (d, J = 8.4 Hz, 1H, ArH), 5.17 (br, 1H, OH); 31P NMR
(162 MHz, CDCl3, 85% H3PO4) δ 26.116; 13C NMR
(100 MHz, CDCl3) δ 141.8, 136.5, 134.4, 133.7, 133.24,
133.22, 133.1, 132.39, 132.35, 130.5, 130.2, 129.8, 129.0,
128.9, 128.6, 128.4, 127.6, 127.3, 127.2, 127.1, 127.0, 126.6,
124.2, 123.7, 123.0, 112.6, 110.4; IR (CH2Cl2) ν: 3359, 3055,
2924, 1623, 1513, 1435, 1269, 1098, 972, 937, 814, 743, 692
cm−1; HRMS–ESI: [M + NH4]+: calcd for C32H27AuClNOP,
704.1179; found, 704.1170.
Supporting Information
Supporting Information File 1
Experimental procedures and characterization date of
compounds.
Gold complex (S)-22 has been prepared by the same reaction
procedure as gold complex (S)-18 in 91% yield. A single crystal
grown from complex (S)-22 in a saturated solution of CH2Cl2/
pentane was suitable for X-ray crystal analysis. white solid;
[α]D20 −80.7 (c 0.95, CH2Cl2); 1H NMR (400 MHz, CDCl3,
TMS) δ 8.27 (d, J = 8.8 Hz, 1H, ArH), 8.05 (d, J = 8.4 Hz, 1H,
ArH), 7.90 (d, J = 8.0 Hz, 1H, ArH), 7.84 (d, J = 8.4 Hz, 1H,
ArH), 7.67 (d, J = 8.4 Hz, 1H, ArH), 7.62–7.57 (m, 1H, ArH),
7.47 (t, J = 7.6 Hz, 1H, ArH), 7.40–7.35 (m, 4H, ArH),
7.28–7.24 (m, 2H, ArH), 7.22–7.12 (m, 6H, ArH), 6.97 (d,
J = 7.6 Hz, 2H, ArH), 6.92 (t, J = 7.2 Hz, 2H, ArH), 6.88 (d,
J = 7.6 Hz, 1H, ArH), 6.84 (d, J = 8.8 Hz, 1H, ArH), 6.77 (t,
J = 7.6 Hz, 2H, ArH); 31P NMR (162 MHz, CDCl3, 85%
H3PO4) δ 22.898, 22.825, 22.751, 22.697; 13C NMR (100 MHz,
CDCl3) δ 151.4, 134.6, 134.4, 134.1, 133.9, 133.7, 133.5,
133.2, 133.1, 131.5, 131.44, 131.37, 131.35, 131.25, 129.9,
129.3, 129.04, 128.98, 128.92, 128.89, 128.87, 128.85, 128.84,
128.7, 128.64, 128.59, 128.51, 128.4, 128.3, 128.2, 127.8,
127.5, 126.81, 126.80, 126.6, 126.5, 126.47, 126.1, 126.0,
[http://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-9-261-S1.pdf]
Supporting Information File 2
Chemical information file of compound (S)-15a.
[http://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-9-261-S2.cif]
Supporting Information File 3
Chemical information file of compound (S)-15b.
[http://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-9-261-S3.cif]
Supporting Information File 4
Chemical information file of compound (S)-18.
[http://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-9-261-S4.cif]
2230

Beilstein J. Org. Chem. 2013, 9, 2224–2232.
14.Shapiro, N. D.; Toste, F. D. Synlett 2010, 675–691.
doi:10.1055/s-0029-1219369
Supporting Information File 5
15.Melhado, A. D.; Brenzovich, W. E., Jr.; Lackner, A. D.; Toste, F. D.
J. Am. Chem. Soc. 2010, 132, 8885–8887. doi:10.1021/ja1034123
16.Benitez, D.; Tkatchouk, E.; Gonzalez, A. Z.; Goddard, W. A., III;
Toste, F. D. Org. Lett. 2009, 11, 4798–4801. doi:10.1021/ol9018002
17.Shapiro, N. D.; Shi, Y.; Toste, F. D. J. Am. Chem. Soc. 2009, 131,
11654–11655. doi:10.1021/ja903863b
Chemical information file of compound (S)-21.
[http://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-9-261-S5.cif]
Supporting Information File 6
18.Tkatchouk, E.; Mankad, N. P.; Benitez, D.; Goddard, W. A., III;
Toste, F. D. J. Am. Chem. Soc. 2011, 133, 14293–14300.
doi:10.1021/ja2012627
Chemical information file of compound (S)-23.
[http://www.beilstein-journals.org/bjoc/content/
supplementary/1860-5397-9-261-S6.cif]
19.Mauleón, P.; Zeldin, R. M.; González, A. Z.; Toste, F. D.
J. Am. Chem. Soc. 2009, 131, 6348–6349. doi:10.1021/ja901649s
20.Hashmi, A. S. K.; Hengst, T.; Lothschütz, C.; Rominger, F.
Adv. Synth. Catal. 2010, 352, 1315–1337.
Acknowledgements
doi:10.1002/adsc.201000126
Financial support from the Shanghai Municipal Committee of
Science and Technology (08dj1400100-2), the Fundamental
Research Funds for the Central Universities, the National Basic
Research Program of China (973)-2010CB833302, the Funda-
mental Research Funds for the Central Universities, and the
National Natural Science Foundation of China (21072206,
21121062, 21121062, 20902019, 20472096, 20872162,
20672127, 20732008, 20821002, and 20702013) are gratefully
acknowledged.
21.Kusama, H.; Karibe, Y.; Onizawa, Y.; Iwasawa, N.
Angew. Chem., Int. Ed. 2010, 49, 4269–4272.
doi:10.1002/anie.201001061
22.Teng, T.-M.; Liu, R.-S. J. Am. Chem. Soc. 2010, 132, 9298–9300.
doi:10.1021/ja1043837
23.Mukherjee, A.; Dateer, R. B.; Chaudhuri, R.; Bhunia, S.; Karad, S. N.;
Liu, R.-S. J. Am. Chem. Soc. 2011, 133, 15372–15375.
doi:10.1021/ja208150d
24.Jurberg, I. D.; Odabachian, Y.; Gagosz, F. J. Am. Chem. Soc. 2010,
132, 3543–3552. doi:10.1021/ja9100134
25.Bolte, B.; Gagosz, F. J. Am. Chem. Soc. 2011, 133, 7696–7699.
doi:10.1021/ja202336p
References
26.Ye, L.; Wang, Y.; Aue, D. H.; Zhang, L. J. Am. Chem. Soc. 2012, 134,
31–34. doi:10.1021/ja2091992
1. Corma, A.; Leyva-Pérez, A.; Sabater, M. J. Chem. Rev. 2011, 111,
1657–1712. doi:10.1021/cr100414u
27.Hashmi, A. S. K.; Braun, I.; Nösel, P.; Schädlich, J.; Wieteck, M.;
Rudolph, M.; Rominger, F. Angew. Chem., Int. Ed. 2012, 51,
4456–4460. doi:10.1002/anie.201109183
2. Li, Z.; Brouwer, C.; He, C. Chem. Rev. 2008, 108, 3239–3265.
doi:10.1021/cr068434l
3. Krause, N.; Winter, C. Chem. Rev. 2011, 111, 1994–2009.
doi:10.1021/cr1004088
28.Barluenga, J.; Sigüeiro, R.; Vicente, R.; Ballesteros, A.; Tomás, M.;
Rodríguez, M. A. Angew. Chem., Int. Ed. 2012, 51, 10377–10381.
doi:10.1002/anie.201205051
4. Nolan, S. P. Acc. Chem. Res. 2011, 44, 91–100.
doi:10.1021/ar1000764
29.Mukherjee, P.; Widenhoefer, R. A. Chem.–Eur. J. 2013, 19,
3437–3444. doi:10.1002/chem.201203987
5. Gaillard, S.; Cazin, C. S. J.; Nolan, S. P. Acc. Chem. Res. 2012, 45,
778–787. doi:10.1021/ar200188f
30.Melhado, A. D.; Amarante, G. W.; Wang, Z. J.; Luparia, M.; Toste, F. D.
J. Am. Chem. Soc. 2011, 133, 3517–3527. doi:10.1021/ja1095045
31.Liu, B.; Li, K.-N.; Luo, S.-W.; Huang, J.-Z.; Pang, H.; Gong, L.-Z.
J. Am. Chem. Soc. 2013, 135, 3323–3326. doi:10.1021/ja3110472
32.Liu, X.-Y.; Che, C.-M. Org. Lett. 2009, 11, 4204–4207.
doi:10.1021/ol901443b
6. Rudolph, M.; Hashmi, A. S. K. Chem. Soc. Rev. 2012, 41, 2448–2462.
doi:10.1039/C1CS15279C
7. Wegner, H. A.; Auzias, M. Angew. Chem., Int. Ed. 2011, 50,
8236–8247. doi:10.1002/anie.201101603
8. Huang, H.; Zhou, Y.; Liu, H. Beilstein J. Org. Chem. 2011, 7, 897–936.
doi:10.3762/bjoc.7.103
33.Alonso, I.; Trillo, B.; López, F.; Montserrat, S.; Ujaque, G.; Castedo, L.;
Lledós, A.; Mascareñas, J. L. J. Am. Chem. Soc. 2009, 131,
13020–13030. doi:10.1021/ja905415r
9. Bandini, M. Chem. Soc. Rev. 2011, 40, 1358–1367.
doi:10.1039/C0CS00041H
10.Cheon, C. H.; Kanno, O.; Toste, F. D. J. Am. Chem. Soc. 2011, 133,
13248–13251. doi:10.1021/ja204331w
34.Briones, J. F.; Davies, H. M. L. J. Am. Chem. Soc. 2012, 134,
11916–11919. doi:10.1021/ja304506g
11.Sethofer, S. G.; Mayer, T.; Toste, F. D. J. Am. Chem. Soc. 2010, 132,
8276–8277. doi:10.1021/ja103544p
35.González, A. Z.; Toste, F. D. Org. Lett. 2010, 12, 200–203.
doi:10.1021/ol902622b
12.Rudolph, M. Applications of Gold-Catalyzed Reactions to Natural
Product Synthesis. In Modern Gold Catalyzed Synthesis;
Hashmi, A. S. K.; Toste, F. D., Eds.; Wiley-VCH: Weinheim, Germany,
2012; pp 331–362.
36.González, A. Z.; Benitez, D.; Tkatchouk, E.; Goddard, W. A., III;
Toste, F. D. J. Am. Chem. Soc. 2011, 133, 5500–5507.
doi:10.1021/ja200084a
37.Rodríguez, L.-I.; Roth, T.; Fillol, J. L.; Wadepohl, H.; Gade, L. H.
Chem.–Eur. J. 2012, 18, 3721–3728. doi:10.1002/chem.201103140
38.Qian, D.; Zhang, J. Chem.–Eur. J. 2013, 19, 6984–6988.
doi:10.1002/chem.201301208
13.Hubbert, C.; Hasmi, A. S. K. Gold-Catalyzed Aldol and Related
Reactions. In Modern Gold Catalyzed Synthesis; Hashmi, A. S. K.;
Toste, F. D., Eds.; Wiley-VCH: Weinheim, Germany, 2012;
pp 237–261.
39.Ye, L.; He, W.; Zhang, L. Angew. Chem., Int. Ed. 2011, 50, 3236–3239.
doi:10.1002/anie.201007624
2231

Beilstein J. Org. Chem. 2013, 9, 2224–2232.
40.Suárez-Pantiga, S.; Hernández-Díaz, C.; Rubio, E.; González, J. M.
Angew. Chem., Int. Ed. 2012, 51, 11552–11555.
65.Zhang, R.; Xu, Q.; Mei, L.-y.; Li, S.-k.; Shi, M. Tetrahedron 2012, 68,
3172–3178. doi:10.1016/j.tet.2012.02.060
doi:10.1002/anie.201206461
66.Li, Z.; Zhang, J.; Brouwer, C.; Yang, C.-G.; Reich, N. W.; He, C.
Org. Lett. 2006, 8, 4175–4178. doi:10.1021/ol0610035
67.Zhang, J.; Yang, C.-G.; He, C. J. Am. Chem. Soc. 2006, 128,
1798–1799. doi:10.1021/ja053864z
41.Liu, F.; Qian, D.; Li, L.; Zhao, X.; Zhang, J. Angew. Chem., Int. Ed.
2010, 49, 6669–6672. doi:10.1002/anie.201003136
42.Bandini, M.; Eichholzer, A. Angew. Chem., Int. Ed. 2009, 48,
9533–9537. doi:10.1002/anie.200904388
68.Kitahara, H.; Kamiya, I.; Sakurai, H. Chem. Lett. 2009, 38, 908–909.
doi:10.1246/cl.2009.908
43.Faustino, H.; Alonso, I.; Mascareñas, J. L.; López, F.
Angew. Chem., Int. Ed. 2013, 52, 6526–6530.
69.Reznichenko, A. L.; Hultzsch, K. C. Organometallics 2013, 32,
1394–1408. doi:10.1021/om3010614
doi:10.1002/anie.201302713
44.Butler, K. L.; Tragni, M.; Widenhoefer, R. A. Angew. Chem., Int. Ed.
2012, 51, 5175–5178. doi:10.1002/anie.201201584
45.Alonso, I.; Faustino, H.; López, F.; Mascareñas, J. L.
Angew. Chem., Int. Ed. 2011, 50, 11496–11500.
70.Turnpenny, B. W.; Hyman, K. L.; Chemler, S. R. Organometallics 2012,
31, 7819–7822. doi:10.1021/om300744m
71.Chapurina, Y.; Ibrahim, H.; Guillot, R.; Kolodziej, E.; Collin, J.;
Trifonov, A.; Schulz, E.; Hannedouche, J. J. Org. Chem. 2011, 76,
10163–10172. doi:10.1021/jo202009q
doi:10.1002/anie.201105815
46.Wang, Y.-M.; Kuzniewski, C. N.; Rauniyar, V.; Hoong, C.; Toste, F. D.
J. Am. Chem. Soc. 2011, 133, 12972–12975. doi:10.1021/ja205068j
47.Alcarazo, M.; Stork, T.; Anoop, A.; Thiel, W.; Fürstner, A.
Angew. Chem., Int. Ed. 2010, 49, 2542–2546.
72.Manna, K.; Xu, S.; Sadow, A. D. Angew. Chem., Int. Ed. 2011, 50,
1865–1868. doi:10.1002/anie.201006163
73.Ayinla, R. O.; Gibson, T.; Schafer, L. L. J. Organomet. Chem. 2010,
696, 50–60. doi:10.1016/j.jorganchem.2010.07.023
74.Hannedouche, J.; Collin, J.; Trifonov, A.; Schulz, E.
J. Organomet. Chem. 2011, 696, 255–262.
doi:10.1002/anie.200907194
48.Francos, J.; Grande-Carmona, F.; Faustino, H.; Iglesias-Sigüenza, J.;
Díez, E.; Alonso, I.; Fernández, R.; Lassaletta, J. M.; López, F.;
Mascareñas, J. L. J. Am. Chem. Soc. 2012, 134, 14322–14325.
doi:10.1021/ja3065446
doi:10.1016/j.jorganchem.2010.09.013
75.Shen, X.; Buchwald, S. L. Angew. Chem., Int. Ed. 2010, 49, 564–567.
doi:10.1002/anie.200905402
49.Handa, S.; Slaughter, L. M. Angew. Chem., Int. Ed. 2012, 51,
2912–2915. doi:10.1002/anie.201107789
76.Horrillo-Martínez, P.; Hultzsch, K. C. Tetrahedron Lett. 2009, 50,
2054–2056. doi:10.1016/j.tetlet.2009.02.069
50.Yang, J.; Zhang, R.; Wang, W.; Zhang, Z.; Shi, M.
Tetrahedron: Asymmetry 2011, 22, 2029–2038.
77.Zi, G. J. Organomet. Chem. 2010, 696, 68–75.
doi:10.1016/j.jorganchem.2010.07.034
doi:10.1016/j.tetasy.2011.12.004
51.Wang, W.; Yang, J.; Wang, F.; Shi, M. Organometallics 2011, 30,
3859–3869. doi:10.1021/om2004404
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2011, 7, 555–564. doi:10.3762/bjoc.7.64
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53.Wang, F.; Li, S.; Qu, M.; Zhao, M.; Liu, L.; Shi, M.
Beilstein J. Org. Chem. 2012, 8, 726–731. doi:10.3762/bjoc.8.81
54.Pérez-Galán, P.; Delpont, N.; Herrero-Gómez, E.; Maseras, F.;
Echavarren, A. M. Chem.–Eur. J. 2010, 16, 5324–5332.
doi:10.1002/chem.200903507
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55.Ooi, T.; Ohmatsu, K.; Maruoka, K. J. Am. Chem. Soc. 2007, 129,
2410–2411. doi:10.1021/ja063051q
The license is subject to the Beilstein Journal of Organic
Chemistry terms and conditions:
56.Jiang, Y.-Q.; Shi, Y.-L.; Shi, M. J. Am. Chem. Soc. 2008, 130,
7202–7203. doi:10.1021/ja802422d
(http://www.beilstein-journals.org/bjoc)
57.Teller, H.; Corbet, M.; Mantilli, L.; Gopakumar, G.; Goddard, R.;
Thiel, W.; Fürstner, A. J. Am. Chem. Soc. 2012, 134, 15331–15342.
doi:10.1021/ja303641p
The definitive version of this article is the electronic one
which can be found at:
58.Kim, J. H.; Park, S.-W.; Park, S. R.; Lee, S.; Kang, E. J.
Chem.–Asian J. 2011, 6, 1982–1986. doi:10.1002/asia.201100135
59.Li, H.; Lee, S. D.; Widenhoefer, R. A. J. Organomet. Chem. 2011, 696,
316–320. doi:10.1016/j.jorganchem.2010.09.045
doi:10.3762/bjoc.9.261
60.Bartolome, C.; García-Cuadrado, D.; Ramiro, Z.; Espinet, P.
Organometallics 2010, 29, 3589–3592. doi:10.1021/om100507r
61.Zhang, Z.; Bender, C. F.; Widenhoefer, R. A. J. Am. Chem. Soc. 2007,
129, 14148–14149. doi:10.1021/ja0760731
62.Zhang, Z.; Bender, C. F.; Widenhoefer, R. A. Org. Lett. 2007, 9,
2887–2889. doi:10.1021/ol071108n
63.LaLonde, R. L.; Sherry, B. D.; Kang, E. J.; Toste, F. D.
J. Am. Chem. Soc. 2007, 129, 2452–2453. doi:10.1021/ja068819l
64.Kitahara, H.; Sakurai, H. J. Organomet. Chem. 2011, 442–449.
doi:10.1016/j.jorganchem.2010.08.038
2232