Paper
5 mg) and K
Dalton Transactions
1
2
CO
3
(3 eq., 0.21 mmol, 28 mg) were charged into through Celite, evaporation of the solvent and trituration with
a scintillation vial along with a magnetic stir bar, followed by 10 mL of pentane followed by filtration afforded the product
1
3
addition of 1 mL of EtOH. The suspension was stirred at 40 °C as a white solid (56 mg, 96%). H NMR (300 MHz, CDCl ) δ
1
1
for 16 h and the solvent was evaporated under reduced 3.60 (d, JH–H = 15.0 Hz, 1H, CHHS), 2.99 (d, JH–H = 15.0 Hz,
CSA
pressure. Addition of 5 mL of benzene permitted filtration 1H, CHHS), 2.87–2.69 (m, 1H, CH ), 2.57–2.24 (m, 20H), 2.04
through Celite, evaporation of the solvent afforded the product (s, 11H), 1.89 (d,
) δ 1.47–1.30 (m, 1H), 1.17 (s, 3H, CH
.70–7.63 (m, 2H, 2,6-CH ), 7.48 (d, J = 7.5 Hz, 2H, 3,5- NMR (101 MHz, CDCl ) δ 216.0 (CvO), 58.6 (CCH S), 48.0
2
JH–H = 18.2 Hz, 1H), 1.83–1.57 (m, 20H),
1
13
as a white solid (42 mg, 81%). H NMR (400 MHz, CDCl
3
3
), 0.87 (s, 3H, CH
3
).
C
Ph
2
7
3
2
Ph
1
CH ), 2.49 (br s, 18H, CH
2
CP), 2.06 (br s, 9H, CH), 1.89–1.68 (CH
2
S), 47.3 (d, JC–P = 18.1 Hz, CP), 42.9 (br s, CH
2
CP), 42.9
1
3
2
CSA
CSA
3
Ad
(m, 18H, CH
2
). C NMR (101 MHz, CDCl
3
) δ 182.6 (d, JC–P
=
(C
H
2
), 36.4 (C
H
2
), 29.1 (d,
J
C–P = 8.6 Hz, C H), 27.2
Ph
2
CSA
CSA
31
1
C
4
2
03.4 Hz, C–Au), 139.4 (2,6-CH ), 127.0 (q, JC–F = 31.4 Hz, (C H ), 25.0 (C H), 20.4 (CH ), 20.0 (CH ). P NMR
2
3
3
Ph
1
Ph
CF
3
), 125.1 (q, JC–F = 271.5 Hz, CF
6.4 (d, JC–P = 10.6 Hz, CP), 43.0 (br s, CH
9.2 (d, J = 8.3 Hz, CH). P NMR (162 MHz, CDCl ) δ 79.3.
3
), 123.6 (m, 3,5-CH ), (162 MHz, CDCl
CP), 36.7 (CH ), 60AuO PS: C 55.55, H 6.99; found: C 55.33, H 6.86.
[Au(PAd )(OPh)] (13). [Au(PAd )(p-OMePh)] (10) (0.07 mmol,
3
) δ 79.3. Elemental analysis calcd (%) for
1
2
2
C
40
H
4
3
31
19
F
3
3
3
NMR (471 MHz, CDCl
49AuF P: C 57.07, H 6.34; found: C 57.14, H 6.48.
Au(PAd )(p-OMePh)] (10). [Au(PAd )Cl] (0.075 mmol, of C H . The suspension was stirred at 60 °C for 2 h and the
3
) δ −62.3. Elemental analysis calcd for 50 mg), phenol (0.07 mmol, 6.7 mg) and a stir bar were
C
37
H
3
charged into a scintillation vial, followed by addition of 1 mL
[
3
3
6
6
5
1
0 mg), (4-methoxyphenyl)boronic acid (1.2 eq., 0.09 mmol, solvent was evaporated under reduced pressure to afford a
1
2 3 3
4 mg), K CO (3 eq., 0.225 mmol, 31 mg) and a sir bar were white solid (47 mg, 96%). H NMR (400 MHz, CDCl ) δ
Ph
Ph
charged into a scintillation vial, followed by addition of 1 mL 7.18–7.11 (m, 2H, 3,5-CH ), 7.05–6.98 (m, 2H, 2,6-CH ),
of acetone. The suspension was stirred at 60 °C for 16 h and 6.65–6.58 (m, 1H, 3-CH ), 2.44 (br s, 18H, CH
the solvent was evaporated under reduced pressure. Addition 9H, CH), 1.75 (m, 18H, CH
of 5 mL of benzene permitted filtration through Celite, evapor- 167.8 (C O), 129.8 (3,5-C H), 118.6 (d, J = 1.6 Hz, 2,6-C H),
Ph
2
CP), 2.04 (br s,
1
3
2
). C NMR (101 MHz, CDCl ) δ
3
Ph
Ph
Ph
Ph
1
ation of the solvent afforded the product as a white solid 115.6 (4-C H), 46.8 (d, JC–P = 17.9 Hz, CP), 42.9 (br s, CH
2
CP),
1
3
31
(49 mg, 88%). H NMR (400 MHz, CDCl ) δ 7.54–7.48 (m, 2H, 36.5 (CH ), 29.1 (d, JC–P = 8.6 Hz, CH). P NMR (162 MHz,
3
2
Ph
2,3
Ph
2
,6-CH ), 6.89 (dd, JH–H = 8.3, 1.0 Hz, 2H, 3,5-CH ), 3.78 CDCl ) δ 74.5. Elemental analysis calcd (%) for C H AuOP: C
3
36 50
(
s, 1H, CH
.77 (m, 18H, CH
3
O), 2.49 (br s, 18H, CH
2
CP), 2.04 (br s, 9H, CH), 59.50, H 6.94; found: C 59.13, H 6.56.
1
3
1
2
). C NMR (101 MHz, CDCl
3
) δ 168.9 (d,
[Au(JohnPhos)Cl] (14). In a glovebox [Au(DMS)Cl] (0.36
2
Ph
Ph
J
C–P
4
= 105.3 Hz, C–Au), 157.6 (C O), 139.8 (2,6-CH ), 113.5 mmol, 100 mg) and JohnPhos (1 eq., 0.36 mmol, 104 mg) was
Ph
1
(d, JC–P = 5.7 Hz, 3,5-CH ), 55.3 (CH
3
O), 46.3 (d, JC–P = 10.2 mixed in a scintillation vial. 2 mL of DCM was added and vial
3
Hz, CP), 42.9 (br s, CH CP), 36.8 (CH
CH). P NMR (162 MHz, CDCl ) δ 79.6. Elemental analysis at room temperature. After that solvent was evaporated under
2
2
), 29.2 (d, JC–P = 8.0 Hz, was taken out the glovebox. Reaction mixture was stirred for 4 h
3
1
3
calcd (%) for C37
H52AuOP: C 59.99, H 7.08; found: C 59.93, H reduced pressure and solid was dissolved in minimum amount
7
.22.
of DCM and precipitated with 10 mL of pentane. Precipitate was
[
Au(PAd )(CCPh)] (11). [Au(PAd )(p-OMePh)] (10) (0.08 mmol, filtered on a sintered funnel and washed with 10 mL of pentane
3
3
1
6
0 mg) along with a stir bar were charged into a scintillation to afford a white solid (174 mg, 90%). H NMR (300 MHz,
and phenylacetylene CDCl ) δ 7.90–7.82 (m, 1H, CHAr), 7.62–7.53 (m, 1H, CHAr),
1.1 eq., 0.09 mmol, 9.8 µL). The suspension was stirred at 7.53–7.46 (m, 2H, CH ), 7.46–7.39 (m, 2H, CH ), 7.34–7.28
vial, followed by addition of 1 mL of C
6
H
6
3
(
Ar
Ar
8
3
0 °C for 2 h and volatiles were evaporated under reduced (m, 1H, CHAr), 7.15–7.10 (m, 2H, CHAr), 1.44 (s, 9H, CH ), 1.38
1
31
pressure to afford a white solid (51 mg, 87%). H NMR (s, 9H, CH
3
). P NMR (121 MHz, CDCl
[Au(JohnPhos)OTf] (15). [Au(JohnPhos)Cl] (0.19 mmol, 100
CP), 2.03 (br s, 9H, CH), mg) and AgOTf (1.05 eq., 0.20 mmol, 51 mg) was mixed in a
). C NMR (101 MHz, CDCl ) δ 137.5 (d, dark in a scintillation vial covered with foil. 2 mL of DCM was
3
) δ 59.94.
Ph
(400 MHz, CDCl ) δ 7.55–7.49 (m, 2H, 2,6-CH ), 7.24–7.13 (m,
3
Ph
3
1
H, 3,4,5-CH ), 2.44 (br s, 18H, CH
2
.75 (m, 18H, CH
1
3
2
3
2
Ph
Ph
JC–P = 122.7 Hz, C–Au), 132.5 (2,6-C H), 127.9 (3,5-C H), added reaction mixture was stirred for 4 h at room tempera-
Ph
4
Ph
3
1
2
26.5 (4-C H), 125.5 (d, JC–P = 2.5 Hz, 1-C ), 103.0 (d, JC–P
=
ture. After that reaction mixture was filtered through celite
1
2.2 Hz, CCAu), 46.7 (d,
JC–P = 14.1 Hz, CP), 42.9 (br s, using 5 mL of DCM. Filtrate was evaporated under reduced
3
31
1
CH CP), 36.6 (CH CP), 29.2 (d, J
= 8.3 Hz, CH). P NMR pressure to afford white solid (107 mg, 88%). H NMR (300
2
2
C–P
(
162 MHz, CDCl
3
3
) δ 78.9. Elemental analysis calcd (%) for MHz, CDCl ) δ 7.82–7.89 (m, 1H, CHAr), 7.61–7.51 (m, 3H,
C
38
H
50AuP: C 62.12, H 6.86; found: C 61.95, H 6.63.
CHAr), 7.51–7.43 (m, 2H, CHAr), 7.39–7.33 (m, 1H, CHAr), 7.18–
3
1
[
Au(PAd (CSA)] (12). [Au(PAd )(p-OMePh)] (10) (0.068 mmol, 7.11 (m, 2H, CH ), 1.43 (s, 9H, CH ), 1.38 (s, 9H, CH ).
P
3
3
Ar
3
3
5
0
0
mg), (1S)-(+)-10-camphorsulfonic acid (1.02 eq., NMR (121 MHz, CDCl
3
) δ 57.21 (br s). NMR shifts of the
3
0
.069 mmol, 16 mg) and a stir bar were charged into a scintil- product corresponded the reported values.
lation vial, followed by addition of 1 mL of CHCl . The suspen-
sion was stirred at room temperature for 16 h and then the
solvent was evaporated under reduced pressure. Addition of
3
Catalytic tests
Hydration of 3-hexyne. [Au(PAd
3
)X], 3-hexyne (199 μL,
5
ml of DCM to the solid residue permitted a filtration 1.75 mmol), H O (34.6 μL, 1.925 mmol) and NBu OTf (34.3 mg,
2
4
Dalton Trans.
This journal is © The Royal Society of Chemistry 2020