Supporting Information:Table of content

sTable of contents....................................................................................................................................................................

1. Materials and methods..........................................................................................................................................................

Chemicals...............................................................................................................................................................................

Autoclaves..............................................................................................................................................................................

1. Hydroaminomethylation of dcpd with ammonia...................................................................................................................

2. Orthogonal bis-HAM with dcpd and n-butyl amine................................................................................................................

Influence of temperature and Ruthenium concentration.......................................................................................................

3. Analyse of the side products..................................................................................................................................................

4. Characterization of the Product.............................................................................................................................................

GC – FID and GC-MS...............................................................................................................................................................

NMR........................................................................................................................................................................................

Orthogonal HAM of dcpd with n-butyl amine.........................................................................................................................

TCD-diamine 13......................................................................................................................................................................

TCD-monoamine-mono(butyl)amine 11................................................................................................................................

TCD-di(butyl)amine 10...........................................................................................................................................................

TCD-mono(butyl)amine 6.......................................................................................................................................................

Orthogonal HAM of dcpd with benzylamine..........................................................................................................................

TCD-monoamine-mono(bezyl)amine.....................................................................................................................................

TCD-di(benzyl)amine..............................................................................................................................................................

TCD-mono(benzyl)amine.......................................................................................................................................................

Orthogonal HAM of dcpd with cyclohexylamine....................................................................................................................

TCD-monoamine-mono(cyclohexyl)amine.............................................................................................................................

TCD-di(cyclohexyl)amine........................................................................................................................................................

TCD-mono(cyclohexyl)amine.................................................................................................................................................

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1. Materials and methods

Chemicals

All chemicals were purchased from commercial suppliers like Sigma Aldrich, Acros Organics and were used without further purification. The synthesis gas was used as received from Messer Industriegas GmbH. Selected rhodium catalysts were donated from Umicore AG & Co. KG (Hanau, Germany).

Chemical purity supplierdicyclopentadiene 95 % ACROSToluene 99.9 % VWR Chemicalsn-butyl amine 99 %+ ACROScyclohexylamine 99 % ACROSbenzylamine 99 % ACROS[Rh(octaonate)2]2 98 % UmicoreShvo-catalyst (1-Hydroxytetraphenylcyclopentadienyl-(tetraphenyl-2,4-cyclopentadien-1-one)-μ-hydrotetracarbonyldiruthenium(II))

98 % STREM

NH3 99.98 % Messer IndustriegaseCO:H2 99.99 Messer Industriegase

Autoclaves

The experiments were performed in 45 mL stainless steel autoclaves with magenetic stirring bar (figure S 9, left) as well as in 300 mL Parr-Autoclave (Figure S 9, right).

Figure S 1. 45 mL stainless steel autoclave (left) and 300 mL stainless steel Parr-Autoclave

1. Hydroaminomethylation of dcpd with ammonia.

Table S1 Hydroaminomethylation of dcpd 1 with ammonia

Nr. Iridium precursor Amine IIYield [%]Y1a(hydrogenated dcpd) Y13 (TCD-diamine) Yhighboilers

S1.1 - Triethylamin 0 0 100S1.2 - DABCO 0 0 100S1.3 [Ir(cod)Cl]2 - 79 0 21

Reaction conditions: 1 mmol dcpd 1, 0.5 mol% [Rh(octanoate)2]2, 2.5 mol % [Ir(cod)Cl]2, 10 mmol NH3, 1 mmol Amine II, t = 2 h, 5mL toluene, p = 60 bar syngas (1:1), T = 120 °C, 350 rpm. X1=100%, missing yield is the sum of the high boilers (oligomerisation, aldol condensation products). Yield (Y) is given as sum of the isomers and reported in % determined with dibutylether as internal standard based on GC–FID analysis.

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2. Orthogonal bis-HAM with dcpd and n-butyl amine

Influence of temperature and Ruthenium concentration

0.25:0.25 0.25:0.5 0.25:1 0.5:0.25 0.5:0.5 0.5:1 1:0.25 1:0.5 1:10

10

20

30

40

50

60

70

80

90

100

Yiel

d [%

]

Rh:Ru [mol%] at 120 C°

Y10 Y11 Y12

Figure S 2. Effects of the Shvo-catalyst concentration at 120°C Reaction conditions: 1 mmol dcpd 1, [Rh(octanoate)2]2, Shvo-catalyst, 6 mmol n-butyl amine, t = 3 h, p = 60 bar syngas (1:1), 10 mL toluene, 350 rpm. X1=100%, missing yield is the sum of the high boilers (oligomerisation, aldol condensation products). Yield (Y) is given as sum of the isomers and reported in % determined with dibutylether as internal standard based on GC–FID analysis.

0.25:0.25 0.25:0.5 0.25:1 0.5:0.25 0.5:0.5 0.5:1 1:0.25 1:0.5 1:10

10

20

30

40

50

60

70

80

90

100

Yie

ld [%

]

Rh:Ru [mol%] at 140 C°

Y10 Y11 Y12

Figure S 3. Effects of the Shvo-catalyst concentration at 140°C Reaction conditions: 1 mmol dcpd 1, [Rh(octanoate)2]2, Shvo-catalyst, 6 mmol n-butyl amine, t = 3 h, p = 60 bar syngas (1:1), 10 mL toluene, 350 rpm. X1=100%, missing yield is the sum of the high boilers (oligomerisation, aldol condensation products). Yield (Y) is given as sum of the isomers and reported in % determined with dibutylether as internal standard based on GC–FID analysis.

0.25:0.25 0.25:0.5 0.25:1 0.5:0.25 0.5:0.5 0.5:1 1:0.25 1:0.5 1:10

10

20

30

40

50

60

70

80

90

100

Yie

ld [%

]

Rh:Ru [mol%] at 160 C°

Y10 Y11 Y12

Figure S 4. Effects of the Shvo-catalyst concentration at 160°C Reaction conditions: 1 mmol dcpd 1, [Rh(octanoate)2]2, Shvo-catalyst, 6 mmol n-butyl amine, t = 3 h, p = 60 bar syngas (1:1), 10 mL toluene, 350 rpm. X1=100%, missing yield is the sum of the high boilers (oligomerisation, aldol condensation products). Yield (Y) is given as sum of the isomers and reported in % determined with dibutylether as internal standard based on GC–FID analysis.

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Table S2. Orthogonal tandem reaction of dcpd 1 with n-butyl amine and ammonia combination of hydroaminomethylation and amination

No. dcpd : n-BuNH2 dcpd [g] n-BuNH2 [mL] Toluene [mL]

H2O [mL]

S2.1a 1:6 094. 0.6 70 -S2.2b 1:50 0.94 30 35 -S2.3c 1:42 0.94 35 30 15

Reaction conditions: 7 mmol dcpd 1, 0.25 mol% [Rh(octanoate)2]2, 0.5 mol% Shvo-catalyst, 420 mmol NH3, t = 6 h, p = 60 bar syngas (CO:H2, 1:1), 350 rpm. a) 70 mL toluene, b) 35 mL toluene, c) 15 mL H2O + 30 mL toluene. Conversion of dcpd 1 =100%, missing yield is the sum of the high boilers (oligomerisation, aldol condensation products). Yield (Y) is given as sum of the isomers and reported in % determined with dibutylether as internal standard based on GC–FID analysis.

Table S3. Orthogonal tandem reaction of dcpd 1 with lower substrate concentrations

No. dcpd : n-BuNH2 dcpd: toluene Yield [%] Ratio Prim.: Sec. amine Y10 Y11 Y13

S3.1 1:50 1:95 27 30 14 0.52S3.2a 1:50 1:190 24 30 8 0.33

Reaction conditions: 7 mmol dcpd 1, 0.25 mol% [Rh(octanoate)2]2, 0.5 mol% Shvo-catalyst, 420 mmol NH3, t = 6 h, p = 60 bar syngas (CO:H2, 1:1), 70 mL toluene, 350 rpm. a) 0.5 mmol dcpd 1, 0.25 mol% [Rh(octanoate)2]2, 0.5 mol% Shvo-catalyst, 30 mmol NH3, t = 6 h, p = 60 bar syngas (CO:H2, 1:1), 10 mL toluene, 350 rpm. Conversion of dcpd 1 =100%, missing yield is the sum of the high boilers (oligomerisation, aldol condensation products). Yield (Y) is given as sum of the isomers and reported in % determined with dibutylether as internal standard based on GC–FID analysis.

Table S4. Orthogonal assisted tandem reaction of dcpd 1 with low n-butyl amine concentration and high ammonia concentration and 1 mol% Shvo catalyst

No. dcpd : NH3 dcpd : n-BuNH2 Yield [%] Ratio Prim.: Sec.amine Y10 Y11 Y13

S4.1 1:150 1:3 9 10 6 0.66

Reaction conditions: 1. Hydroaminomethylation Step: 1 mmol dcpd 1, 0.25 mol% [Rh(octanoate)2]2, 1 mol% Shvo-catalyst, 3 mmol n-butyl amine, 15 mL toluene, T = 140 °C, t = 3 h, p = 60 bar syngas (CO:H2, 1:1), 350 rpm. 2. Consecutive splitting of amines step: T = 180 °C, t = 16 h, 150 NH3. Conversion of dcpd 1 = 100%, missing yield is the sum of the high boilers (oligomerisation, aldol condensation products). Yield (Y) is given as sum of the isomers and reported in % determined with dibutylether as internal standard based on GC–FID analysis.

Table S5. Orthogonal assisted tandem reaction of dcpd 1, TCD-Diamine 13 and mix of both as starting materials with and without the addition of ammonia

No. substrate NH3 Yield [%] Ratio Prim.: Sec. amine Y10 Y11 Y13

S5.1a 1 mmol TCD-diamine 1:120 6 24 22 3.66

S5.2 1 mmol TCD-diamine 1:0 9 21 15 1.66

S5.3 0.5 mmol dcpd + 0.5 TCD-diamine 1:120 6 21 22 3.66

S5.4 0.5 mmol dcpd + 0.5 TCD-diamine 1:0 8 21 10 1.25

Reaction conditions: 1. Hydroaminomethylation Step: substrate, 0.25 mol% [Rh(octanoate)2]2, 0.5 mol% Shvo-catalyst, n-butyl amine, 10 mL toluene, 350 rpm, T = 140 °C, t = 3 h, p = 60 bar syngas (CO:H2, 1:1). 2. Consecutive splitting of amines step: T = 180 °C, t = 16 h. Conversion of dcpd 1 = 100%, missing yield is the sum of the high boilers

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(oligomerisation, aldol condensation products). Yield (Y) is given as sum of the isomers and reported in % determined with dibutylether as internal standard based on GC–FID analysis.

Table S6. Investigations of di-butyl amine formation in the absences of substrate

No. substrate Yield [%]Yn-butylformamide Ydi-butylamine Ytri-butylamine

S6.1 no substrate 99 0 0

Reaction conditions: 0.25 mol% [Rh(octanoate)2]2, 0.5 mol% Shvo-catalyst, 42 mmol n-butyl amine, 70 mL toluene, 350 rpm, T = 140 °C, t = 24 h, p = 60 bar syngas (CO:H2, 1:1). Yield (Y) is in % determined with dibutylether as internal standard based on GC–FID analysis.

Table S7. Orthogonal assisted tandem reaction of dcpd with the addition of water in the splitting of amine step

No. Addition of water [mL] Yield [%]Y10 Y11 Y13

S7.1 2.5 13 33 20

S7.2 5 17 30 13

Reaction conditions: 1. Hydroaminomethylation Step: 1 mmol dcpd, 0.25 mol% [Rh(octanoate)2]2, 0.5 mol% Shvo-catalyst, 6 mmol n-butyl amine, 10 mL toluene, 350 rpm, T = 140 °C, t = 3 h, p = 60 bar syngas (CO:H2, 1:1). 2. Consecutive splitting of amines step: 120 mmol NH3, T = 180 °C, t = 16 h. Conversion of dcpd 1 = 100%, missing yield is the sum of the high boilers (oligomerisation, aldol condensation products). Yield (Y) is given as sum of the isomers and reported in % determined with dibutylether as internal standard based on GC–FID analysis.

Table S8. Orthogonal assisted tandem reaction of dcpd 1 with n-butyl amine and addition of ammonia under different reaction concentrations

No. dcpd : n-

BuNH2

Yield [%]Ydi-butylamine

S8.1 1:3 28S8.2 1:6 35S8.3 1:12 14

Reaction conditions: 1. Hydroaminomethylation Step: 1 mmol dcpd 1, 0.25 mol% [Rh(octanoate)2]2, 0.5 mol% Shvo-catalyst, n-butyl amine, 15 mL toluene, 350 rpm, T = 140 °C, t = 3 h, p = 60 bar syngas (CO:H2, 1:1). 2. Consecutive splitting of amines step: T = 180 °C, t = 16 h, 120 NH3. Conversion of dcpd 1 = 100%, missing yield is the sum of the high boilers (oligomerisation, aldol condensation products). Yield (Y) is given as sum of the isomers and reported in % determined with dibutylether as internal standard based on GC–FID analysis.

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3. Analyse of the side products

Figure S 5. IR-Analyse of the side products HAM with dcpd 1 and NH3

Figure S 6. MALDI-TOF spectra of side products of HAM with dcpd 1 and NH3

161.096

203.220

146.002

190.144

-CH2

-NH-C-N-CH2

-NH

-NH

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Figure S 7. MALDI-TOF spectra of side products of HAM with dcpd 1 and NH3

Figure S 8. MALDI-TOF spectra of side products of orthogonal HAM of dcpd 1 with Rhodium and Ruthenium catalyst with n-butyl amine

176178

179178

176

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Figure S 9. MALDI-TOF spectra of side products of orthogonal tandem reaction of dcpd 1 with n-butyl amine and NH3

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4. Characterization of the Product

GC – FID and GC-MS

The GC analysis was done with a GC from Agilent Technologies Inc. model 7890B with a flame ionization detector (FID, 325°C), a HP-column (length: 30m, ø: 0.25mm, film thickness: 0.25 μm)) and an auto sampler. N2 is used as carrier gas (v = 1.0 ml/min, 30 cm/s) with an injection volume 1 μL and a split of 15:1. An example of a typical GC chromatogram of the product solution is shown below. Conversion of substrate and yields were determined with dibutylether as internal standard by GLC.

NMR

The purified products were analysed with NMR. As spectrometer, a Brucer DRX600 (600 MHz) and CDCl3 as solvent was used. The reaction mixture was concentrated and purified by column chromatography (ethyl acetate 1:0 to 1:10).

Orthogonal HAM of dcpd with n-butyl amine

Figure S 10. GC – chromatogram of dcpd and cyclohexylamine

TCD-diamine 13

GC-MS: (EL, 70 eV) m/z [%] = 194.20 (5), 177.19 (80), 165.19 (20), 164.18 (13), 160.10 (50), 149.14 (13), 148.13 (100)147.11 (23), 146.13 (10), 134.10 (13), 133.14 (26), 131.10 (15), 120.10 (31), 119.10 (54), 118.10 (17), 117.10 (21), 107.10 (33), 106.10 (40), 105.10 (43) 1H-NMR (CDCl3, 600 MHz): δ = 0.89 (m, 1H, CH2), 1.15 (s, 4H, NH2), 1.39-1.43 (m, 2H, CH2), 1.48-1.52 (m, 3H, CH2), 1.70-1.71 (m, 3H, CH, CH2), 1.78-1.84 (m, 1H, CH2), 1.93-1.96 (m, 2H, CH), 2.13 (s, 1H, CH), 2.41-2.43 (m, 2H, CH2), 2.49-2.55 (m, 3H, CH, CH2) ppm. 13C-NMR (CDCl3, 600 MHz): δ = 24.6 (1C, CH2), 30.0 (1C, CH2), 33.6 (1C, CH2), 38.28 (1C, CH), 40.7 (1C, CH2), 40.8 (1C, CH), 43.7 (2C, CH), 45.9 (1C, CH), 47.8 (1C, CH2), 47.9 (1C, CH2), 50.2 (1C, CH) ppm.

TCD-monoamine-mono(butyl)amine 11

GC-MS: (EL, 70 ev) m/z [%] = 250.22 (5), 234.14 (9), 207.14 (50), 190.04 (6), 176.11 (7), 165.10 (58), 148.09 (100), 133.05 (12), 119.06 (24), 112.05 (7), 104.99 (17)

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ESI-HRMS: Calculated for C16H31N2 ([M+H]+): 251.24818Measured ([M+H]+): 251.24752

TCD-di(butyl)amine 10

GC-MS (EI, 70 eV): m/z [%] = 306.3 (M+, 20.84), 263.3 (100), 221.20 (66.5), 178.20 (58.18), 152.20 (69.44)ESI-HRMS: Calculated for C20H39N2 ([M+H]+): 307.31078

Measured ([M+H]+): 307.310191H-NMR (CDCl3, 600 MHz): δ = 0.82-0.91 (m, 6H, CH3), 1.06-1.52 (m, 12H, CH, CH2), 1.70-2.32 (m, 7H, CH, CH2), 2.25-2.60 (m, 8H, CH2). 13C-NMR (CDCl3, 150 MHz): δ = 13.94, 20.43, 24.42, 25.25, 29.46, 29.96, 30.34, 32.06, 32.21, 32.29, 34.12, 35.06, 35.23, 38.89, 39.37, 39.79, 40.50, 40.56, 40.72, 40.75, 41.73, 42.19, 43.88, 44.03, 44.60, 45.05, 45.11, 45.80, 49.74, 49.82, 50.02, 51.38, 55.65, 55.90, 56.88.

TCD-mono(butyl)amine 6

GC-MS (EI, 70 eV): m/z [%] = 219.20 (M+, 35.98), 176.20 (100), 105.10 (28.03)

Figure S 11. 1H-NMR of TCD-diamine 13.

Figure S 12. 13C-NMR of TCD-diamine 13.

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Figure S 13. 1H-NMR TCD-di(butyl)amine 10.

Figure S 14. Zoom of 1H-NMR TCD-di(butyl)amine 10.

Figure S 15. 13C-NMR TCD-di(butyl)amine 10.

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Figure S 16. Zoom of 13C-NMR TCD-di(butyl)amine 10.

Orthogonal HAM of dcpd with benzylamine

Figure S 17. GC – chromatogram of dcpd and benzylamine

TCD-monoamine-mono(bezyl)amine

GC-MS (EI, 70 eV): m/z [%] = 284.20 (M+, 7.882), 179.10 (6.695), 148.10 (26.196), 121.10 (9.554), 120.10 (100.000), 119.10 (7.790), 118.10 (8.584), 107.00 (10.581), 106.00 (75.444), 105.00 (6.163)ESI-HRMS: Calculated for C19H29N2 ([M+H]+): 285.23253

Measured ([M+H]+): 285.23213

TCD-di(benzyl)amine

GC-MS (EI, 70 eV): m/z [%] = 374.30 (M+, 11.32), 283.20 (11.35), 268.20 (17.10), 255.20 (13.57), 253.20 ( 19.82), 120.10 (100.00), 119.10 (14.45), 118.10 (19.80), 108.10 (42.51), 107.10 (16.84), 106.10 (58.22)ESI-HRMS: Calculated for C26H35N2 ([M+H]+): 375.27948

Measured ([M+H]+): 375.27921

TCD-mono(benzyl)amine

GC-MS (EI, 70 eV): m/z [%] = 253.2 (M+, 8.29), 121.1 (9.98), 120.1 (100), 118.1 (7.53), 106.1 (9.08)

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Orthogonal HAM of dcpd with cyclohexylamine

Figure S 18. GC – chromatogram of dcpd and cyclohexylamine

TCD-monoamine-mono(cyclohexyl)amine

GC-MS (EI, 70 eV): m/z [%] = 276.20 (M+, 6.17), 233.20 (17.14), 148.10 (7.34), 113.10 ( 7.70), 112.10 (100.00)ESI-HRMS: Calculated for C18H33N2 ([M+H]+): 277.26383

Measured ([M+H]+): 277.26321

TCD-di(cyclohexyl)amine

GC-MS (EI, 70 eV): m/z [%] = 358.40 (M+, 5.07), 315.30 (5.07), 275.30 (6.30), 247.3 (11.86), 204.2 (4.269), 176.2 ( 5.86), 136.2 (7.468), 113.1 (8.116), 112.1 (100)ESI-HRMS: Calculated for C24H43N2 ([M+H]+): 359.34208

Measured ([M+H]+): 359.34155

TCD-mono(cyclohexyl)amine

GC-MS (EI, 70 eV): m/z [%] = 245.30 (M+, 5.95), 202.20 (15.50), 138.10 (7.87),113.10(9.04), 112.20 (100.00)

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