Table 2.
Oxidation of rac‐sec‐allylic alcohols with variants of HMFO.[a]
|
Entry |
Substr. |
Variant |
Conv. [%] |
ee s [%][b] |
E |
|---|---|---|---|---|---|
|
1 |
1 a |
wt |
16 |
19 (R) |
>200 |
|
2 |
1 a |
V465T |
50 |
>99 (R) |
>200 |
|
3 |
1 a |
V465S |
50 |
>99 (R) |
>200 |
|
4 |
1 a |
V465T/W466H |
25 |
33 (R) |
>200 |
|
5 |
1 a |
V367R/W466F |
18 |
21 (R) |
55 |
|
6 |
2 a |
wt |
29 |
25 (R) |
5 |
|
7 |
2 a |
V465T |
50 |
>99 (R) |
>200 |
|
8 |
2 a |
V465S |
50 |
>99 (R) |
>200 |
|
9 |
2 a |
V465T/W466H |
50 |
99 (R) |
>200 |
|
10 |
2 a |
V367R/W466F |
33 |
34 (R) |
8 |
|
11 |
3 a |
wt |
10 |
10 (R) |
21 |
|
12 |
3 a |
V465T |
48 |
94 (R) |
>200 |
|
13 |
3 a |
V465S |
50 |
99 (R) |
>200 |
|
14 |
3 a |
V465T/W466H |
50 |
96 (R) |
>200 |
|
15 |
3 a |
V367R/W466F |
46 |
83 (R) |
>200 |
|
16 |
4 a |
wt |
13 |
14 (R) |
35 |
|
17 |
4 a |
V465T |
48 |
92 (R) |
>200 |
|
18 |
4 a |
V465S |
48 |
96 (R) |
>200 |
|
19 |
4 a |
V465T/W466H |
50 |
98 (R) |
>200 |
|
20 |
4 a |
V367R/W466F |
32 |
45 (R) |
70 |
|
21 |
5 a |
wt |
4 |
2 |
n.d.[c] |
|
22 |
5 a |
V465T |
32 |
44 (R) |
46 |
|
23 |
5 a |
V465S |
38 |
58 (R) |
65 |
|
24 |
5 a |
V465T/W466H |
4 |
n.d.[c] |
n.d.[c] |
|
25 |
5 a |
V367R/W466F |
4 |
n.d.[c] |
n.d.[c] |
[a] Condition: KPi‐buffer (200 mM, pH 7.0) containing the oxidases (14.2 μM final concentration in 500 μL reaction volume in 4 mL glass vials), catalase from Micrococcus lysodeikticus (15 μL, 170000 U/mL), substrate (50 mM). The reaction mixtures were shaken for 16 hours (170 rpm, 21 °C) and extracted with ethyl acetate (2×300 μL), dried with Na2SO4 and analyzed by GC‐FID. Conversions were measured based on area ratio of ketone to substrate. Reactions were conducted in duplicate.
[b] Ees values for 1 a were measured by using GC equipped with chiral column. Ees values for 2 a–5 a were measured by using HPLC equipped with a chiral column.
[c] Not determined due to low conversion.