Table 5.
Oxidation of rac‐allylic alcohols with HMFO V465S in the presence of 5% v/v organic solvents.[a]
|
Entry |
Substr. |
Cosolvents |
Conv. [%] |
ee s [%][b] |
E |
|---|---|---|---|---|---|
|
1 |
1 a |
DMSO |
51 |
>99 (R) |
>200 |
|
2 |
1 a |
isooctane |
50 |
>99 (R) |
>200 |
|
3 |
1 a |
glycerol |
51 |
>99 (R) |
>200 |
|
4 |
1 a |
n‐heptane |
50 |
>99 (R) |
>200 |
|
5 |
1 a |
MeOH |
51 |
>99 (R) |
>200 |
|
6 |
1 a |
EtOH |
51 |
>99 (R) |
>200 |
|
7 |
1 a |
iPrOH |
51 |
>99 (R) |
>200 |
|
8 |
1 a |
2‐butanone |
52 |
>99 (R) |
>200 |
|
9 |
1 a |
acetone |
51 |
>99 (R) |
>200 |
|
10 |
1 a |
DMF |
50 |
>99 (R) |
>200 |
|
11 |
1 a |
dioxane |
50 |
>99 (R) |
>200 |
|
12 |
2 a |
DMSO |
65 |
98 (R) |
14 |
|
13 |
2 a |
isooctane |
49 |
93 (R) |
>200 |
|
14 |
2 a |
glycerol |
51 |
99 (R) |
>200 |
|
15 |
2 a |
n‐heptane |
50 |
95 (R) |
146 |
|
16 |
2 a |
MeOH |
49 |
96 (R) |
>200 |
|
17 |
2 a |
EtOH |
50 |
92 (R) |
79 |
|
18 |
2 a |
iPrOH |
50 |
95 (R) |
146 |
|
19 |
2 a |
2‐butanone |
49 |
85 (R) |
44 |
|
20 |
2 a |
acetone |
48 |
83 (R) |
49 |
|
21 |
2 a |
DMF |
55 |
98 (R) |
41 |
|
22 |
2 a |
dioxane |
50 |
86 (R) |
37 |
|
23 |
3 a |
DMSO |
49 |
74 (R) |
17 |
|
24 |
3 a |
isooctane |
36 |
54 (R) |
84 |
|
25 |
3 a |
glycerol |
72 |
99 (R) |
11 |
|
26 |
3 a |
n‐heptane |
42 |
62 (R) |
24 |
|
27 |
3 a |
MeOH |
38 |
51 (R) |
18 |
|
28 |
3 a |
EtOH |
36 |
54 (R) |
84 |
|
29 |
3 a |
iPrOH |
50 |
70 (R) |
12 |
|
30 |
3 a |
2‐butanone |
42 |
70 (R) |
124 |
|
31 |
3 a |
acetone |
42 |
70 (R) |
124 |
|
32 |
3 a |
DMF |
37 |
56 (R) |
74 |
|
33 |
3 a |
dioxane |
40 |
44 (R) |
7 |
|
34 |
4 a |
DMSO |
67 |
>99 (R) |
14 |
|
35 |
4 a |
isooctane |
63 |
>99 (R) |
18 |
|
36 |
4 a |
glycerol |
55 |
>99 (R) |
49 |
|
37 |
4 a |
n‐heptane |
79 |
>99 (R) |
7 |
|
38 |
4 a |
MeOH |
53 |
>99 (R) |
80 |
|
39 |
4 a |
EtOH |
50 |
>99 (R) |
>200 |
|
40 |
4 a |
iPrOH |
51 |
>99 (R) |
>200 |
|
41 |
4 a |
2‐butanone |
50 |
>99 (R) |
>200 |
|
42 |
4 a |
acetone |
53 |
>99 (R) |
80 |
|
43 |
4 a |
DMF |
52 |
>99 (R) |
116 |
|
44 |
4 a |
dioxane |
58 |
>99 (R) |
31 |
|
45 |
5 a |
DMSO |
17 |
13 (R) |
5 |
|
46 |
5 a |
isooctane |
20 |
20 (R) |
11 |
|
47 |
5 a |
glycerol |
68 |
76 (R) |
4 |
|
48 |
5 a |
n‐heptane |
20 |
19 (R) |
9 |
|
49 |
5 a |
MeOH |
18 |
17 (R) |
9 |
|
50 |
5 a |
EtOH |
11 |
10 (R) |
10 |
|
51 |
5 a |
iPrOH |
19 |
17 (R) |
7 |
|
52 |
5 a |
2‐butanone |
17 |
16 (R) |
10 |
|
53 |
5 a |
acetone |
27 |
30 (R) |
13 |
|
54 |
5 a |
DMF |
22 |
22 (R) |
10 |
|
55 |
5 a |
dioxane |
19 |
19 (R) |
11 |
[a] Condition: KPi‐buffer (200 mM, pH 7.0) containing the oxidases (14.2 μM final concentration in 1 mL reaction volume in 4 mL glass vials), catalase from Micrococcus lysodeikticus (30 μL, 170000 U/mL), the substrate (50 mM), 5% v/v various co‐solvents. The reaction mixtures were shaken for 16 hours (170 rpm, 21 °C) and extracted with ethyl acetate (2×500 μL), dried with Na2SO4 and analyzed by GC‐MS. Conversions were measured based on area ratio of ketone to substrate.
[b] Ees values for 1 a were measured by GC on a chiral phase. ees values for 2 a–5 a were measured by HPLC on a chiral phase.