To each of
the two duplicate Parr autoclave reactors fitted with Teflon inlays
(30 mL total volume) were added Ru/C (5 wt % Ru, 75 mg), Birch sawdust
(500 mg), and MeOH (10 mL). The reactors were closed, evacuated five
times with H2, and subjected to a H2 pressure
of 30 bar at room temperature. The autoclaves were then stirred at
250 °C for 16 h and thereafter filtered through celite into a
round-bottom flask, rinsed with EtOAc, and concentrated in
vacuo. EtOAc (25 mL) was added to the concentrate followed
by sonification for 5 min. Pentane (25 mL) was then introduced, whereafter
the mixture was passed through a short silica dry column (5 cm silica),
rinsing with EtOAc/pentane (1:1, 50 mL) into a cone-shaped flask (100
mL). The concentrate was used in the subsequent step without further
purification. Quantification via GC-MS using dodecane
as an internal standard was carried out for the monomer products,
2-methoxy-4-propylphenol1 (13.9 mg) and 2,6-dimethoxy-4-propylphenol 2 (51.3 mg). This provides a reaction scale of 0.345 mmol
for the subsequent fluorosulfation and cyanation reaction steps.
To chamber A of a two-chamber reactor (20 mL total volume) were added
K2CO3 (143 mg, 1.03 mmol, 3.0 equiv) and the
concentrate from the prior hydrogenolysis reaction (Step I), which
was transferred with MeCN (4 mL × 1 mL). The chamber was sealed
with a screwcap fitted with a Teflon-coated silicone seal. 1,1′-Sulfonylbis(1H-imidazole) (205 mg, 1.03 mmol, 3.0 equiv) and KF (160
mg, 2.76 mmol, 8.0 equiv) were added to chamber B of the two-chamber
reactor. The chamber was sealed with a screwcap fitted with a pierceable
Teflon-coated silicone seal. Trifluoroacetic acid (0.5 mL) was then
added to the closed chamber B via the Teflon-coated
silicone seal and sulfuryl fluoride release was observed within a
minute. The reactor was stirred at room temperature for 16 h, after
which the reaction mixture was passed through celite into a cone-shaped
flask and concentrated in vacuo. Qualitative GC-MS
analysis showed a full conversion of1 and 2 to aryl fluorosulfates 3 and 4 (see the
SI,Figure S4 ). The concentrate was used
in the subsequent step without further purification.
In an argon-filled
glovebox, Pd–XPhos–G4 (14.8 mg,
0.017 mmol, 5 mol %), K2CO3 (143 mg, 1.03 mmol,
3.0 equiv.), and KCN (33.7 mg, 0.517 mmol, 1.5 equiv) were added to
a pressure tube (9 mL total volume). The concentrate from the prior
fluorosulfation reaction (Step II) was also transferred to the tube
with MeCN (2 mL × 1 mL) and 2-MeTHF (2 mL × 1 mL). The chamber
was sealed with a screwcap fitted with a Teflon-coated silicone seal
and stirred at 70 °C for 16 h. The reaction mixture was then
evaporated onto celite and purified by flash column chromatography
to yield aryl nitrile products5 (13.6 mg, 5.4 wt %)
as a colorless liquid (eluted with pentane to pentane/EtOAc 95:5)
and6 (44.4 mg, 18 wt %) as a colorless crystalline solid
(eluted with Pentane/EtOAc 80:20).
the two duplicate Parr autoclave reactors fitted with Teflon inlays
(30 mL total volume) were added Ru/C (5 wt % Ru, 75 mg), Birch sawdust
(500 mg), and MeOH (10 mL). The reactors were closed, evacuated five
times with H2, and subjected to a H2 pressure
of 30 bar at room temperature. The autoclaves were then stirred at
250 °C for 16 h and thereafter filtered through celite into a
round-bottom flask, rinsed with EtOAc, and concentrated in
vacuo. EtOAc (25 mL) was added to the concentrate followed
by sonification for 5 min. Pentane (25 mL) was then introduced, whereafter
the mixture was passed through a short silica dry column (5 cm silica),
rinsing with EtOAc/pentane (1:1, 50 mL) into a cone-shaped flask (100
mL). The concentrate was used in the subsequent step without further
purification. Quantification via GC-MS using dodecane
as an internal standard was carried out for the monomer products,
2-methoxy-4-propylphenol
for the subsequent fluorosulfation and cyanation reaction steps.
To chamber A of a two-chamber reactor (20 mL total volume) were added
K2CO3 (143 mg, 1.03 mmol, 3.0 equiv) and the
concentrate from the prior hydrogenolysis reaction (Step I), which
was transferred with MeCN (4 mL × 1 mL). The chamber was sealed
with a screwcap fitted with a Teflon-coated silicone seal. 1,1′-Sulfonylbis(1H-imidazole) (205 mg, 1.03 mmol, 3.0 equiv) and KF (160
mg, 2.76 mmol, 8.0 equiv) were added to chamber B of the two-chamber
reactor. The chamber was sealed with a screwcap fitted with a pierceable
Teflon-coated silicone seal. Trifluoroacetic acid (0.5 mL) was then
added to the closed chamber B via the Teflon-coated
silicone seal and sulfuryl fluoride release was observed within a
minute. The reactor was stirred at room temperature for 16 h, after
which the reaction mixture was passed through celite into a cone-shaped
flask and concentrated in vacuo. Qualitative GC-MS
analysis showed a full conversion of
SI,
in the subsequent step without further purification.
In an argon-filled
glovebox, Pd–XPhos–G4 (14.8 mg,
0.017 mmol, 5 mol %), K2CO3 (143 mg, 1.03 mmol,
3.0 equiv.), and KCN (33.7 mg, 0.517 mmol, 1.5 equiv) were added to
a pressure tube (9 mL total volume). The concentrate from the prior
fluorosulfation reaction (Step II) was also transferred to the tube
with MeCN (2 mL × 1 mL) and 2-MeTHF (2 mL × 1 mL). The chamber
was sealed with a screwcap fitted with a Teflon-coated silicone seal
and stirred at 70 °C for 16 h. The reaction mixture was then
evaporated onto celite and purified by flash column chromatography
to yield aryl nitrile products
as a colorless liquid (eluted with pentane to pentane/EtOAc 95:5)
and
(eluted with Pentane/EtOAc 80:20).
