Table 2 Rh1/PNP-ND catalyzed hydroformylation of substituted vinyl arenes.

From: Phosphorus coordinated Rh single-atom sites on nanodiamond as highly regioselective catalyst for hydroformylation of olefins

Entry

Substrate

Conv. (%)

Sel.aCHO (%)

b/lb

1

2-methylstyrene

>99

99

7.3:1

2

3-methylstyrene

>99

99

6.9:1

3

4-methylstyrene

>99

99

6.7:1

4

4-tert-butylstyrene

>99

99

8.8:1

5

2,5-dimethylstyrene

>99

99

7.8:1

6

4-methoxystyrene

>99

99

7.5:1

7

3,4-dimethoxystyrene

>99

99

8.1:1

8

2-fluorostyrene

68

99

10.1:1

9

3-fluorostyrene

>99

98

13.3:1

10

4-fluorostyrene

>99

99

10.2:1

11

2-chlorostyrene

44

99

11.5:1

(>99)c

(99)

(13.3:1)

12

3-chlorostyrene

>99

99

15.7:1

13

4-chlorostyrene

>99

99

10.1:1

14

2-bromostyrene

>99c

96

13.7:1

15

3-bromostyrene

>99c

95

13.6:1

16

4-bromostyrene

>99c

98

11.5:1

18

4-hydroxystyrene

>99

99

7.9:1

19d

2-vinylnaphthalene

98

99

6.2:1

  1. Reaction conditions: 3 mmol substrate, 50 mg catalyst (Rh loading = 0.5 wt%), 15 mL toluene, 15 mL H2O, 3.0 MPa syngas (CO/H2 = 1), 50 °C, 24 h.
  2. aThe selectivity for the aldehydes products.
  3. bThe molar ratio of branched aldehydes/linear aldehydes.
  4. c60 h.
  5. d36 h.