hydroaminoalkylation of sterically hindered alkenes with n,n · s1 hydroaminoalkylation of...

S1

Hydroaminoalkylation of sterically hindered alkenes with N,N-

dimethyl anilines using a scandium catalyst

Jianhong Su, Yiqun Zhou, Xin Xu*

Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical

Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China

*[email protected]

Supporting Information

General Procedures: All experiments were carried out under a dry Argon

atmosphere using standard Schlenk techniques or in a glovebox. Solvents (including

deuterated solvents used for NMR) were dried and distilled prior to use. NMR spectra

were recorded on a Bruker 400 MHz and a Bruker 600 MHz spectrometer. Chemical

shifts were reported as δ units with reference to the residual solvent resonance or an

external standard. The assignments of NMR data were supported by 1D and 2D NMR

experiments. Elemental analysis data was recorded on a Carlo-Erba EA-1110

instrument. High resolution mass spectrometry was measured with a BRUKER

micrOTOF-Q III. [PhNMe2H][B(C6F5)4] was purchased from Strem. Ligand precursor

HL1 and Sc(CH2SiMe3)3(THF)22 were prepared according to the literature procedures.

All substrates were distilled from CaH2 or molecular sieves before use.

Hydroaminoalkylation products 4a,3 4m,4 6b,5 6c5, 86 and 97 have been reported in

literatures.

References:

1. S. A. Patil, P. A. Medina, J. W. Ziller and B. D. Faflman, SpringerPlus., 2013, 2, 32.

2. M. F. Lappert and R. Pearce, J. Chem. Soc. Chem. Commun., 1973, 126.

3. T. Rische and P. Eilbracht, Synthesis., 1997, 11, 1331.

4. S. Mignani, R. Merenyi, Z. Janousek and H. G. Viehe, Tetrahedron., 1985, 41, 769.

5. I. Sorribes, J. R. Cabrero-Antonino, C. Vicent, K. Junge and M. Beller, J. Am. Chem. Soc., 2015,

137, 13580.

6. Z. Lu, A. Wilsily and G. C. Fu, J. Am. Chem. Soc., 2011, 133, 8154.

7. G. Song, G. Luo, J. Oyamada, Y. Luo and Z. Hou, Chem. Sci., 2016, 7, 5265.

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2018

S2

Characterization of complex 1:

Scheme S1.

1H, 1H GCOSY (600 MHz / 600 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =

7.20 / 6.99 (m-Ph / p-Ph), 3.15 / 1.35, 1.15 (CHMe2 / CHMe2, CHMe2).

1H, 13C GHSQC (600 MHz / 151 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.20 / 130.2,

125.1 (o-Ph, m-Ph), 7.10 / 127.3, 124.6 (p-PhDipp, m-PhDipp), 6.99 / 126.1 (p-Ph), 5.00

/ 98.7 (N=CCH), 3.15 / 28.7 (CHMe2), 1.72 / 23.4 (NCMe), 1.56 / 23.1 (NCMe), 1.35

/ 25.4 (CHMe2), 1.15 / 24.2 (CHMe2), 0.12 / 45.0 (ScCH2Si), 0.11 / 3.4 (CH2SiMe3).

1H, 13C GHMBC (600 MHz / 151 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C

= 7.20 / 145.7, 130.2, 126.1 (o-Ph, m-Ph / i-Ph, m-Ph, p-Ph), 7.10 / 142.8, 140.7,

124.6, 28.7 (m-PhDipp, p-PhDipp / o-PhDipp, i-PhDipp, m-PhDipp, CHMe2), 6.99 / 130.2,

125.1 (p-Ph / m-Ph, o-Ph), 5.00 / 168.2, 165.4, 145.7, 140.7, 23.4, 23.1 (N=CCH /

N=C, N=C, i-Ph, i-PhDipp, NCMe, NCMe), 3.15 / 142.8, 140.7, 124.6 (CHMe2 / o-

PhDipp, i-PhDipp, m-PhDipp), 1.72 / 165.4, 98.7 (NCMe / N=C, N=CCH), 1.35 / 142.8,

24.2, 28.7 (CHMe2 / o-PhDipp, CHMe2, CHMe2), 0.12 / 45.0, 3.40 (ScCH2Si,

CH2SiMe3).

S3

Fig S1. 1H NMR (600 MHz, C6D6, 298 K)

Fig S2. 13C{1H} NMR (151 MHz, C6D6, 298 K)

S4

X-ray crystal structure analysis of complex 1: formula C31H51N2ScSi2, M = 552.88,

clear colourless crystal, 0.5 x 0.35 x 0.30 mm, a = 38.238(2), b = 10.4410(5), c =

17.4643(9) Å, β = 98.199(2)°, V = 6901.3(6) Å3, ρcalc = 1.064gcm-3, μ = 0.302mm-1,

empirical absorption correction (0.6687 ≤ T ≤ 0.7456), Z = 8, monoclinic, space

group C 2/c, λ = 0.71073 Å, T = 120(2) K, Multi-scan, 47739 reflections collected (±h,

±k, ±l), 7927 independent (R(int) = 0.0070) and 5641 observed reflections [I>2σ(I)],

337 refined parameters, R = 0.0425, wR2 = 0.0976, max. (min.) residual electron

density 0.384(-0.311) e.Å-3, hydrogen atoms were calculated and refined as riding

atoms.

Fig S3. Molecular structure of complex 1.

S5

Characterization of hydroaminoalkylation products:

4a was isolated as pale yellow oil (117 mg, 91% yield).

HRMS (ESI) m/z calcd. For C17H22N [M + H]+: 240.1747; found: 240.1740.

1H NMR (400 MHz, C6D6, 298 K): δ = 7.24 (m, 2H, m-PhN), 7.18 (m, 2H, m-Ph),

7.09 (m, 1H, p-Ph), 7.02 (m, 2H, o-Ph), 6.78 (m, 1H, p-PhN), 6.60 (m, 2H, o-PhN),

2.98 (m, 2H, CH2N), 2.52 (s, 3H, CH3N), 2.43 (m, 1H, CHCH3), 1.65 (m, 2H,

NCH2CH2), 1.09 (d, 3JHH = 7.0 Hz, 3H, CHCH3).

13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 149.7 (i-PhN), 147.1 (i-Ph), 129.5 (m-

PhN), 128.8 (m-Ph), 127.3 (o-Ph), 126.5 (p-Ph), 116.6 (p-PhN), 112.8 (o-PhN), 51.2

(CH2N), 38.2 (CHCH3), 38.0 (CH3N), 34.6 (NCH2CH2), 23.0 (CHCH3).

Fig S4. 1H NMR (400 MHz, C6D6, 298 K)

S6


4b was isolated as pale yellow oil (117 mg, 85% yield).



6.95 (m, 2H, o-Ph), 6.77 (m, 1H, p-PhN), 6.60 (m, 2H, o-PhN), 3.02 (m, 2H, CH2N),

2.54 (s, 3H, CH3N), 2.45 (m, 1H, CH3CH), 2.17 (s, 3H, CH3), 1.68 (m, 2H,


13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 149.7 (i-PhN), 144.1 (i-Ph), 135.6 (p-

Ph), 129.5 (m-PhN, overlapped with m-Ph), 127.2 (o-Ph), 116.5 (p-PhN), 112.8 (o-

PhN), 51.2 (CH2N), 38.1 (CH3N), 37.8 (CHCH3), 34.7 (NCH2CH2), 23.2 (CHCH3),

21.1 (CH3).


7.24 / 6.77, 6.60 (m-PhN / p-PhN, o-PhN), 7.03 / 6.95 (m-Ph / o-Ph), 1.68 / 3.02, 2.45

(NCH2CH2 / NCH2, CH3CH).

S7

1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.24 / 129.5 (m-

PhN), 7.03 / 129.5 (m-Ph), 6.95 / 127.2 (o-Ph), 6.77 / 116.5 (p-PhN), 6.60 / 112.8 (o-

PhN), 3.02 / 51.2 (CH2N), 2.54 / 38.1 (CH3N), 2.45 / 37.8 (CHCH3), 2.17 / 21.1

(CH3), 1.68 / 34.7 (NCH2CH2), 1.10 / 23.2 (CHCH3).


= 7.24 / 149.7, 129.5, 112.8 (m-PhN / i-PhN, m-PhN, o-Ph), 3.02 / 149.7, 38.1, 37.8,

34.7 (NCH2 / i-PhN, CH3N, CH3CH, NCH2CH2), 2.45 / 144.1, 51.2, 34.7, 23.2

(CH3CH / i-Ph, CH2N, NCH2CH2, CHCH3).

Fig S6. 1H NMR (400 MHz, C6D6, 298 K)

S8


4c was isolated as pale yellow oil (146 mg, 86% yield).


1H NMR (400 MHz, C6D6, 298 K): δ = 7.56 (m, 2H, 6-C6H5), 7.51 (m, 2H, 3-C6H4),

7.28 (m, 4H, m-PhN, 7-C6H5), 7.19 (m, 1H, 8-C6H5), 7.09 (m, 2H, 2-C6H4), 6.81 (m,

1H, p-PhN), 6.67 (m, 2H, o-PhN), 3.07 (m, 2H, CH2N), 2.57 (s, 3H, CH3N), 2.50 (m,

1H, CHCH3), 1.72 (m, 2H, NCH2CH2), 1.15 (d, 3JHH = 7.0 Hz, 3H, CHCH3).

13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 149.7 (i-PhN), 146.2 (1-C6H4), 141.6 (5-

C6H5), 139.7 (4-C6H4), 129.5 (m-PhN), 129.1 (7-C6H5), 127.7 (2-C6H4), 127.6 (3-

C6H4), 127.4 (8-C6H5), 127.3 (6-C6H5), 116.6 (p-PhN), 112.8 (o-PhN), 51.2 (CH2N),

38.1 (CH3N), 37.8 (CHCH3), 34.6 (NCH2CH2), 23.0 (CHCH3).

S9


7.28 / 7.56, 7.28, 7.19, 6.81, 6.67 (m-PhN / 6-C6H5, 7-C6H5, 8-C6H5, p-PhN, o-PhN),

7.51 / 7.09 (3-C6H4 / 2-C6H4), 1.72 / 3.07, 2.50 (NCH2CH2 / CH2N, CHCH3).

1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.56 / 127.3 (6-

C6H5), 7.51 / 127.6 (3-C6H4), 7.28 / 129.5, 129.1 (m-PhN, 7-C6H5), 7.19 / 127.4 (8-

C6H5), 7.09 / 127.7 (2-C6H4), 6.81 / 116.6 (p-PhN), 6.67 / 112.8 (o-PhN), 3.07 / 51.2

(CH2N), 2.57 / 38.1 (CH3N), 2.50 / 37.8 (CHCH3), 1.72 / 34.6 (NCH2CH2), 1.15 /

23.0 (CHCH3).


= 7.56 / 139.7, 127.4 (6-C6H5 / 4-C6H4, 8-C6H5), 3.07 / 149.7, 38.1, 37.8 (CH2N / i-

PhN, CH3N, CHCH3).

Fig S8. 1H NMR (400 MHz, C6D6, 298 K)

S10


4d was isolated as pale yellow oil (122 mg, 81% yield).


1H NMR (400 MHz, C6D6, 298 K): δ = 7.37 (m, 2H, m-Ph), 7.24 (m, 2H, m-PhN),

7.00 (m, 2H, o-Ph), 6.77 (m, 1H, p-PhN), 6.60 (m, 2H, o-PhN), 5.42 (s, 1H, C=CH2),

5.03 (s, 1H, C=CH2), 3.02 (m, 2H, CH2N), 2.53 (s, 3H, CH3N), 2.45 (m, 1H, CHCH3),

2.02 (s, 3H, CCH3), 1.68 (m, 2H, NCH2CH2), 1.11 (d, 3JHH = 7.0 Hz, 3H, CHCH3).

13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 149.7 (i-PhN), 146.4 (i-Ph), 143.4

(C=CH2), 139.6 (i-Ph), 129.5 (m-PhN), 127.2 (o-Ph), 126.1 (m-Ph), 116.6 (p-PhN),

112.8 (o-PhN), 112.0 (C=CH2), 51.2 (CH2N), 38.1 (CH3N), 37.8 (CHCH3), 34.6

(NCH2CH2), 23.0 (CHCH3), 22.0 (CCH3).

S11


7.37 / 7.00 (m-Ph / o-Ph), 7.24 / 6.77, 6.60 (m-PhN / p-PhN, o-PhN), 2.45 / 1.68, 1.11

(CHCH3 / NCH2CH2, CHCH3).


Ph), 7.24 / 129.5 (m-PhN), 7.00 / 127.2 (o-Ph), 6.77 / 116.6 (p-PhN), 6.60 / 112.8 (o-

PhN), 5.42 / 112.0 (C=CH2), 5.03 / 112.0 (C=CH2), 3.02 / 51.2 (CH2N), 2.53 / 38.1

(CH3N), 2.45 / 37.8 (CHCH3), 2.02 / 22.0 (CCH3), 1.68 / 34.6 (NCH2CH2), 1.11 /

23.0 (CHCH3).


= 7.37 / 146.4, 143.4, 126.1 (m-Ph / i-Ph, C=CH2, m-Ph), 7.24 / 149.7, 129.5, 116.6,

112.8 (m-PhN / i-PhN, m-PhN, p-PhN, o-PhN), 3.02 / 149.7, 38.1, 37.8 (CH2N / i-

PhN, CH3N, CHCH3).

Fig S10. 1H NMR (400 MHz, C6D6, 298 K)

S12


4e was isolated as pale yellow oil (142 mg, 91% yield).


1H NMR (400 MHz, C6D6, 298 K): δ = 7.65 (m, 3H, 3-C10H7, 5-C10H7, 8-C10H7),

7.47 (m, 1H, 10-C10H7), 7.31 (m, 1H, 7-C10H7), 7.26 (m, 1H, 6-C10H7), 7.23 (m, 2H,

m-PhN), 7.14 (m, 1H, 2-C10H7), 6.77 (m, 1H, p-PhN), 6.60 (m, 2H, o-PhN), 3.00 (m,

2H, CH2N), 2.59 (m, 1H, CHCH3), 2.51 (s, 3H, CH3N), 1.74 (m, 2H, NCH2CH2), 1.15

(d, 3JHH = 7.0 Hz, 3H, CHCH3).

13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 149.7 (i-PhN), 144.5 (1-C10H7), 134.3

(9-C10H7), 133.0 (4-C10H7), 129.5 (m-PhN), 128.6 (3-C10H7), 128.1 (overlapped with

solvent, 5-C10H7), 128.0 (8-C10H7), 126.3 (7-C10H7), 125.8 (10-C10H7), 125.7 (2-

C10H7), 125.6 (6-C10H7), 116.6 (p-PhN), 112.9 (o-PhN), 51.2 (NCH2), 38.3 (CHCH3),

38.1 (CH3N), 34.4 (NCH2CH2), 23.0 (CHCH3).

S13


7.65 / 7.31, 7.14 (3-C10H7, 5-C10H7, 8-C10H7 / 7-C10H7, 2-C10H7), 7.23 / 6.77, 6.60 (m-

PhN / p-PhN, o-PhN), 2.59 / 1.74, 1.12 (CHCH3 / NCH2CH2, CHCH3).


128.1, 128.0 (3-C10H7, 5-C10H7, 8-C10H7), 7.47 / 125.8 (10-C10H7), 7.31 / 126.3 (7-

C10H7), 7.26 / 125.6 (6-C10H7), 7.23 / 129.5 (m-PhN), 7.14 / 125.7 (2-C10H7), 6.77 /

116.6 (p-PhN), 6.60 / 112.9 (o-PhN), 3.00 / 51.2 (NCH2), 2.59 / 38.3 (CHCH3), 2.51 /

38.1 (CH3N), 1.74 / 34.4 (NCH2CH2), 1.15 / 23.0 (CHCH3).


= 7.65 / 144.5, 134.3, 133.0, 128.6, 126.3, 125.8, 125.6 (3-C10H7, 5-C10H7, 8-C10H7 /

1-C10H7, 9-C10H7, 4-C10H7, 3-C10H7, 7-C10H7, 10-C10H7, 6-C10H7), 7.23 / 149.7, 129.5,

112.9 (m-PhN / i-PhN, m-PhN, o-PhN), 3.00 / 149.7, 38.3, 38.1 (CH2N / i-PhN,

CHCH3, CH3N).

Fig S12. 1H NMR (400 MHz, C6D6, 298 K)

S14


4f was isolated as pale yellow oil (117 mg, 86 % yield).



6.91 (m, 3H, o-Ph, p-Ph), 6.77 (m, 1H, p-PhN), 6.60 (m, 2H, o-PhN), 3.01 (m, 2H,

NCH2), 2.53 (s, 3H, CH3N), 2.47 (m, 1H, CH3CH), 2.18 (s, 3H, PhCH3), 1.69 (m, 2H,



Ph), 129.5 (m-PhN), 128.8 (m-Ph), 128.1 (overlapped with solvent, p-Ph), 127.3 (o-

Ph), 124.3 (o-Ph), 116.5 (p-PhN), 112.8 (o-PhN), 51.2 (CH2N), 38.1 (CH3N), 38.0

(CH3CH), 34.6 (NCH2CH2), 23.1 (CHCH3), 21.6 (CH3).

S15


7.24 / 6.77, 6.60 (m-PhN / p-PhN, o-PhN), 1.69 / 3.01, 2.47 (NCH2CH2 / NCH2,

CH3CH), 2.46 / 1.69, 1.10 (CH3CH / NCH2CH2, CHCH3).


PhN), 7.14 / 128.8 (m-Ph), 6.91 / 128.1, 127.3, 124.3 (p-Ph, o-Ph, o-Ph), 6.77 / 116.5

(p-PhN), 6.60 / 112.8 (o-PhN), 3.01 / 51.2 (CH2N), 2.53 / 38.1 (CH3N), 2.47 / 38.1

(CH3CH), 2.18 / 21.6 (CH3), 1.69 / 34.6 (NCH2CH2), 1.10 / 23.1 (CHCH3).


= 7.24 / 149.7, 129.5, 116.5, 112.8 (m-PhN / i-PhN, m-PhN, p-PhN, o-Ph), 3.01 /

149.7, 38.1, 38.0, 34.6 (NCH2 / i-PhN, CH3N, CH3CH, NCH2CH2), 2.47 / 147.1,

124.3, 51.2, 34.6, 23.1 (CH3CH / i-Ph, o-Ph, CH2N, NCH2CH2, CHCH3).

Fig S14. 1H NMR (400 MHz, C6D6, 298 K)

S16


4g was isolated as pale yellow oil (117 mg, 78 % yield).


1H NMR (400 MHz, C6D6, 298 K): δ = 7.33 (m, 1H, p-Ph), 7.29 (m, 1H, o-Ph), 7.24

(m, 2H, m-PhN), 7.16 (overlapped with solvent, 1H, m-Ph), 6.96 (m, 1H, o-Ph), 6.77

(m, 1H, p-PhN), 6.59 (m, 2H, o-PhN), 5.42 (s, 1H, C=CH2), 5.05 (s, 1H, C=CH2),

2.98 (m, 2H, CH2N), 2.52 (s, 3H, CH3N), 2.46 (m, 1H, CHCH3), 2.03 (s, 3H, CCH3),

1.68 (m, 2H, NCH2CH2), 1.09 (d, 3JHH = 7.0 Hz, 3H, CHCH3).

13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 149.7 (i-PhN), 147.1 (i-Ph), 143.9

(C=CH2), 142.0 (i-Ph), 129.5 (m-PhN), 128.8 (m-Ph), 126.3 (o-Ph), 124.6 (p-Ph),

124.0 (o-Ph), 116.6 (p-PhN), 112.8 (o-PhN), 112.6 (C=CH2), 51.2 (CH2N), 38.3

(CHCH3), 38.0 (CH3N), 34.5 (NCH2CH2), 23.2 (CHCH3), 22.1 (CCH3).

S17


7.24 / 6.76, 6.59 (m-PhN / p-PhN, o-PhN), 7.16 / 7.33, 6.96 (m-Ph / p-Ph, o-Ph), 1.68

/ 2.98, 2.46 (NCH2CH2 / CH2N, CHCH3).

1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.33 / 124.6 (p-

Ph), 7.29 / 124.0 (o-Ph), 7.24 / 129.5 (m-PhN), 7.16 / 128.8 (m-Ph), 6.96 / 126.3 (o-

Ph), 6.77 / 116.6 (p-PhN), 6.59 / 112.8 (o-PhN), 5.42 / 112.6 (C=CH2), 5.05 / 112.6

(C=CH2), 2.99 / 51.2 (CH2N), 2.52 / 38.0 (CH3N), 2.46 / 38.3 (CHCH3), 2.03 / 22.1

(CCH3), 1.09 / 23.2 (CHCH3).


= 7.33 / 143.9, 124.6, 124.0, 126.3 (p-Ph / C=CH2, p-Ph, o-Ph, o-Ph), 6.96 / 124.6,

124.0, 38.3 (o-Ph / p-Ph, o-Ph, CHCH3), 2.98 / 149.7, 38.3, 38.0, 34.5 (CH2N / i-PhN,

CHCH3, CH3N, NCH2CH2).

Fig S16. 1H NMR (400 MHz, C6D6, 298 K)

S18


4h was isolated as pale yellow oil (158 mg, 73% yield).

HRMS (ESI) m/z calcd. For C28H37N2 [M + H]+: 401.2951; found: 401.2960.


6.98 (m, 1H, o1-Ph), 6.93 (m, 2H, o2-Ph), 6.76 (m, 2H, p-PhN), 6.61 (m, 4H, o-PhN),

3.03 (m, 4H, CH2N), 2.54 (s, 6H, CH3N), 2.47 (m, 2H, CHCH3), 1.70 (m, 4H,



PhN), 129.0 (m-Ph), 126.0 (o1-Ph), 125.0 (o2-Ph), 116.6 (p-PhN), 112.8 (o-PhN),

51.2 (CH2N), 38.3 (CHCH3), 38.1 (CH3N), 34.6 (NCH2CH2), 23.2 (CHCH3).


7.22 / 6.76, 6.61 (m-PhN / p-PhN, o-PhN), 7.18 / 6.93 (m-Ph / o-Ph), 1.70 / 3.03, 2.47

(NCH2CH2 / CH2N, CHCH3).

S19


PhN), 7.18 / 129.0 (m-Ph), 6.98 / 126.0 (o1-Ph), 6.93 / 125.0 (o2-Ph), 6.76 / 116.6 (p-

PhN), 6.61 / 112.8 (o-PhN), 3.03 / 51.2 (CH2N), 2.54 / 38.1 (CH3N), 2.47 / 38.3

(CHCH3), 1.70 / 34.6 (NCH2CH2), 1.13 / 23.2 (CHCH3).


= 7.22 / 149.7, 126.0, 112.8 (m-PhN / i-PhN, m-PhN, o-PhN), 6.98 / 125.0, 38.3 (o1-

Ph / o2-Ph, CHCH3), 3.03 / 149.7, 38.3, 38.1, 34.6 (CH2N / i-PhN, CHCH3, CH3N,

NCH2CH2).

Fig S18. 1H NMR (400 MHz, C6D6, 298 K)

S20


4i was isolated as pale yellow oil (168 mg, 78% yield).


1H NMR (400 MHz, C6D6, 298 K): δ = 7.24 (m, 4H, m-PhN), 7.03 (s, 4H, Ph), 6.77

(m, 2H, p-PhN), 6.61 (m, 4H, o-PhN), 3.04 (m, 4H, CH2N), 2.54 (s, 6H, CH3N), 2.48

(m, 2H, CHCH3), 1.70 (m, 4H, NCH2CH2), 1.12 (d, 3JHH = 7.0 Hz, 6H, CHCH3).


PhN), 127.4 (Ph), 116.6 (p-PhN), 112.8 (o-PhN), 51.2 (CH2N), 38.1 (CH3N), 37.8

(CHCH3), 34.8 (NCH2CH2), 23.1 (CHCH3).


7.24 / 6.77, 6.61 (m-PhN / p-PhN, o-PhN), 2.48 / 1.70, 1.12 (CHCH3 / NCH2CH2,

CHCH3).


PhN), 7.03 / 127.4 (Ph), 6.77 / 116.6 (p-PhN), 6.61 / 112.8 (o-PhN), 3.04 / 51.2

S21

(CH2N), 2.54 / 38.1 (CH3N), 2.48 / 37.8 (CHCH3), 1.70 / 34.8 (NCH2CH2), 1.12 /

23.1 (CHCH3).


= 7.24 / 149.7, 129.5, 112.8 (m-PhN / i-PhN, m-PhN, o-PhN), 7.03 / 144.9, 127.4 (Ph

/ i-Ph, Ph), 3.04 / 149.7, 38.1, 37.8 (CH2N / i-PhN, CH3N, CHCH3).

Fig S20. 1H NMR (400 MHz, C6D6, 298 K)

S22


4j was isolated as pale yellow oil (102 mg, 75% yield).




2.94 (m, 2H, CH2N), 2.48 (s, 3H, CH3N), 2.16 (m, 1H, CHCH2CH3), 1.71 (m, 1H,

NCH2CH2), 1.59 (m, 1H, NCH2CH2), 1.40 (m, 2H, CHCH2CH3), 0.66 (t, 3JHH = 7.4

Hz, 3H, CHCH2CH3).



(CH2N), 45.9 (CHCH2CH3), 38.0 (CH3N), 33.0 (NCH2CH2), 30.3 (CHCH2CH3), 12.3

(CHCH2CH3).

S23



/ 2.94, 2.16 (NCH2CH2 / CH2N, CHCH2CH3), 1.40 / 2.16, 0.66 (CHCH2CH3 /

CHCH2CH3, CHCH2CH3).


PhN), 7.12 / 128.7 (m-Ph), 7.05 / 126.5 (p-Ph), 6.94 / 128.0 (o-Ph), 6.73 / 116.5 (p-

PhN), 6.53 / 112.7 (o-PhN), 2.94 / 51.2 (CH2N), 2.48 / 38.0 (CH3N), 2.16 / 45.9

(CHCH2CH3), 1.71 / 33.0 (NCHCH2), 1.59 / 33.0 (NCHCH2), 1.40 / 30.3

(CHCH2CH3), 0.66 / 12.3 (CHCH2CH3).


= 7.19 / 149.7, 129.5, 112.7 (m-PhN / i-PhN, m-PhN, o-PhN), 7.12 / 145.2, 128.0 (m-

Ph / i-Ph, o-Ph), 2.94 / 149.7, 45.9, 38.0, 33.0 (CH2N / i-PhN, CHCH2CH3, CH3N,

NCHCH2), 1.40 / 145.2, 45.9, 33.0, 12.3 (CHCH2CH3 / i-Ph, CHCH2CH3, NCHCH2,

CHCH2CH3).

Fig S22. 1H NMR (400 MHz, C6D6, 298 K)

S24


4k was isolated as pale yellow oil (91 mg, 63% yield).




2.99 (m, 2H, CH2N), 2.53 (s, 3H, CH3N), 2.33 (m, 1H, CHCH2CH3), 1.76 (m, 1H,

NCH2CH2), 1.63 (m, 1H, NCH2CH2), 1.40 (m, 2H, CHCH2CH2CH3), 1.08 (m, 2H,

CHCH2CH2CH3), 0.77 (t, 3JHH = 7.4 Hz, 3H, CHCH2CH2CH3).

13C{1H} NMR (101 MHz, C6D6, 298 K): δ =149.7 (i-PhN), 145.5 (i-Ph), 129.5 (m-


(CH2N), 43.9 (CHCH2CH2CH3), 39.8 (CHCH2CH2CH3), 38.1 (CH3N),

33.3(NCHCH2), 21.0 (CHCH2CH2CH3), 14.3 (CHCH2CH2CH3).

S25



/ 2.99, 2.33 (NCH2CH2 / CH2N, CHCH2CH2CH3), 1.40 / 2.33, 1.08 (CHCH2CH2CH3 /

CHCH2CH2CH3, CHCH2CH2CH3).


PhN), 7.18 / 128.7 (m-Ph), 7.09 / 126.5 (p-Ph), 7.01 / 128.0 (o-Ph), 6.77 / 116.6 (p-

PhN), 6.58 / 112.8 (o-PhN), 2.99 / 51.2 (CH2N), 2.53 / 38.1 (CH3N), 2.33 / 43.9

(CHCH2CH2CH3), 1.76 / 33.3 (NCHCH2), 1.63 / 33.0 (NCHCH2), 1.40 / 39.8

(CHCH2CH2CH3), 1.08 / 21.0 (CHCH2CH2CH3), 0.77 / 14.3 (CHCH2CH2CH3).


= 7.23 / 149.7, 129.5, 112.8 (m-PhN / i-PhN, m-PhN, o-PhN), 7.18 / 145.5, 128.0 (m-

Ph / i-Ph, o-Ph), 2.99 / 149.7, 43.9, 38.1, 33.3 (CH2N / i-PhN, CHCH2CH2CH3,

CH3N, NCHCH2), 1.40 / 145.5, 43.9, 33.3, 14.3 (CHCH2CH2CH3 / i-Ph,

CHCH2CH2CH3, NCHCH2, CHCH2CH2CH3).

Fig S24. 1H NMR (400 MHz, C6D6, 298 K)

S26


4l was isolated as pale yellow oil (83 mg, 58% yield).


1H NMR (400 MHz, C6D6, 298 K): δ = 7.26 (m, 2H, m-PhN), 7.03 (m, 3H, 1-C10H11,

2-C10H11, 3-C10H11), 6.96 (m, 1H, 4-C10H11), 6.78 (m, 1H, p-PhN), 6.68 (m, 2H, o-

PhN), 3.15 (m, 2H, CH2N), 2.61 (m, 1H, 10-C10H11), 2.57 (s, 3H, CH3N), 2.55 (m, 2H,

C10H11), 1.84 (m, 1H, C10H11), 1.61 (m, 3H, NCH2CH2, C10H11), 1.47 (m, 2H, C10H11).

13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 149.8 (i-PhN), 140.8 (5-C10H11), 137.1

(6-C10H11), 129.6 (4-C10H11), 129.5 (m-PhN), 128.8 (1-C10H11), 126.1 (2-C10H11),

126.0 (3-C10H11), 116.7 (p-PhN), 112.9 (o-PhN), 50.9 (CH2N), 38.0 (CH3N), 35.9

(10-C10H11), 33.5 (C10H11), 29.9 (C10H11), 28.0 (NCH2CH2), 20.3 (C10H11).

S27


7.26 / 6.78, 6.68 (m-PhN / p-PhN, o-PhN), 7.03 / 6.96 (1-C10H11, 2-C10H11, 3-C10H11 /

4-C10H11), 2.61 / 1.61 (10-C10H11 / NCH2CH2, C10H11).


PhN), 7.03 / 128.8, 126.1, 126.0 (1-C10H11, 2-C10H11, 3-C10H11), 6.96 / 129.6 (4-

C10H11), 6.78 / 116.7 (p-PhN), 6.68 / 112.9 (o-PhN), 3.15 / 50.9 (CH2N), 2.61 / 35.9

(10-C10H11), 2.57 / 38.0 (CH3N), 2.55 / 29.9 (C10H11), 1.84 / 33.5 (C10H11), 1.61 / 33.5,

28.0, 20.3 (C10H11, NCH2CH2, C10H11), 1.47 / 28.0, 20.3 (NCH2CH2, C10H11).


= 7.26 / 149.8, 129.5, 112.9 (m-PhN / i-PhN, m-PhN, o-PhN), 3.15 / 149.8, 38.0, 35.9

(CH2N / i-PhN, CH3N, 10-C10H11).

Fig S26. 1H NMR (400 MHz, C6D6, 298 K)

S28


4m was isolated as pale yellow oil (122 mg, 75% yield).


1H NMR (400 MHz, C6D6, 298 K): δ = 7.23 (m, 2H, m-PhN), 7.10 (m, 8H, o-Ph, m-

Ph), 7.02 (m, 2H, p-Ph), 6.78 (m, 1H, p-PhN), 6.58 (m, 2H, o-PhN), 3.71 (t, 3JHH =

7.8 Hz, 1H, CHPh2), 3.06 (m, 2H, CH2N), 2.52 (s, 3H, CH3N), 2.14 (m, 2H,

NCH2CH2).


Ph), 128.8 (m-Ph), 128.2 (o-Ph), 126.5 (p-Ph), 116.7 (p-PhN), 112.8 (o-PhN), 51.4

(CH2N), 49.2 (CHPh2), 38.1 (CH3N), 32.4 (NCH2CH2).

S29

Fig S28. 1H NMR (400 MHz, C6D6, 298 K)

S30




1H NMR (400 MHz, C6D6, 298 K): δ = 7.25 (m, 2H, m-Ph), 6.78 (m, 1H, p-Ph), 6.73

(m, 2H, o-Ph), 3.01 (s, 2H, CH2N), 2.65 (s, 3H, CH3N), 1.54 (m, 4H, C5H8), 1.40 (m,

2H, C5H8), 1.20 (m, 2H, C5H8), 0.84 (s, 3H, CH3).

13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 151.2 (i-Ph), 129.3 (m-Ph), 116.4 (p-Ph),

112.5 (o-Ph), 61.8 (CH2N), 46.4 (CCH3), 40.8 (CH3N), 37.9 (C5H8), 25.0 (CCH3),

24.1 (C5H8).


7.25 / 6.78, 6.73 (m-Ph / p-Ph, o-Ph), 3.01 / 2.65 (CH2N / CH3N).


Ph), 6.78 / 116.4 (p-Ph), 6.73 / 112.5 (o-Ph), 3.01 / 61.8 (CH2N), 2.65 / 40.8 (CH3N),

1.54 / 24.1 (C5H8), 1.40 / 37.9 (C5H8), 1.20 / 37.9 (C5H8), 0.84 / 25.0 (CCH3).


= 7.25 / 151.2, 129.3, 116.4, 112.5 (m-Ph / i-Ph, m-Ph, p-Ph, o-Ph), 3.01 / 151.2, 46.4,

40.8, 25.0 (CH2N / i-Ph, CCH3, CH3N, CCH3).

S31

Fig S30. 1H NMR (400 MHz, C6D6, 298 K)

S32





(m, 2H, o-Ph), 2.90 (s, 2H, CH2N), 2.66 (s, 3H, CH3N), 1.35 (m, 9H, C6H10), 1.09 (m,

1H, C6H10), 0.82 (s, 3H, CH3).


112.7 (o-Ph), 64.8 (CH2N), 41.8 (CH3N), 37.9 (CCH3), 36.7 (C6H10), 26.7 (C6H10),

22.5 (CCH3), 22.3 (C6H10).


7.26 / 6.78, 6.74 (m-Ph / p-Ph, o-Ph).

1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.26 / 129.2(m-

Ph), 6.78 / 116.4 (p-Ph), 6.74 / 112.7 (o-Ph), 2.90 / 64.8 (CH2N), 2.66 / 41.8 (CH3N),

1.38 / 36.7, 26.7, 22.3 (C6H10, C6H10, C6H10), 1.09 / 26.7 (C6H10), 0.82 / 22.5 (CCH3).


= 7.26 / 151.3, 129.2, 116.4, 112.7 (m-Ph / i-Ph, m-Ph, p-Ph, o-Ph), 2.90 / 151.3, 41.8,

36.7, 22.5 (CH2N / i-Ph, CH3N, C6H10, CCH3).

S33

Fig S32. 1H NMR (400 MHz, C6D6, 298 K)


S34




(m, 2H, o-Ph), 2.96 (m, 2H, CH2N), 2.62 (s, 3H, CH3N), 1.69 (m, 1H, NCH2CH),

1.21 (m, 6H, CH2), 0.84 (t, 3JHH = 7.0 Hz, 3H, CH3), 0.79 (t, 3JHH = 7.5 Hz, 3H, CH3).


112.7 (o-Ph), 57.4 (CH2N), 39.3 (CH3N), 38.0 (NCH2CH), 33.8 (CH2), 24.4 (CH2),

20.1 (CH2), 14.81 (CH2CH3), 11.0 (CH2CH3).


7.26 / 6.78, 6.69 (m-Ph / p-Ph, o-Ph), 2.96 / 1.68 (CH2N / CH2CH), 1.69 / 2.96, 1.21

(CH2CH / CH2N, CH2).


Ph), 6.78 / 116.5 ( p-Ph), 6.69 / 112.7 (o-Ph), 2.96 / 57.4 (CH2N), 2.62 / 39.3 (CH3N),

1.69 / 38.0 (NCH2CH), 1.21 / 33.8, 24.4, 20.1 (CH2, CH2, CH2), 0.84 / 14.81

(CH2CH3), 0.79 / 11.0 (CH2CH3).


= 7.26 / 112.7, 129.5, 150.3 (m-Ph / o-Ph, m-Ph, i-Ph), 6.78 / 112.7, 129.5 ( p-Ph / o-

Ph, m-Ph), 2.96 / 150.3, 39.3, 38.0, 33.8, 24.4 (CH2N / i-Ph, CH3N, NCH2CH, CH2,

CH2).

S35

Fig S34. 1H NMR (400 MHz, C6D6, 298 K)

Fig S35.13C{1H} NMR (101 MHz, C6D6, 298 K)

S36



1H NMR (400 MHz, C6D6, 298 K) δ(ppm): 7.28 (m, 2H, m-Ph), 6.79 (m, 1H, p-Ph),

6.67 (m, 2H, o-Ph), 2.98 (d, 3JHH = 8.1 Hz, 2H, CH2N), 2.62 (s, 3H, CH3N), 2.09 (m,

1H, CH2CH), 1.61-1.44 (m, 4H, C5H9), 1.43-1.30 (m, 2H, C5H9), 1.12-0.90 (m, 2H,

C5H9).


112.7 (o-Ph), 57.9 (CH2N), 39.2 (CH2CH), 38.9 (CH3N), 30.9 (C5H9), 25.3 (C5H9).

Fig S36. 1H NMR (400 MHz, C6D6, 298 K)

S37





(m, 2H, o-Ph), 2.88 (d, 3JHH = 6.9 Hz, 2H, CH2N), 2.62 (s, 3H, CH3N), 1.61 (m, 6H,

C6H11), 1.06 (m, 3H, C6H11), 0.72 (m, 2H, C6H11).


112.4 (o-Ph), 59.8 (CH2N), 39.4 (CH3N), 37.1 (C6H11), 31.5 (C6H11), 26.9 (C6H11),

26.4 (C6H11).

S38

Fig S38. 1H NMR (400 MHz, C6D6, 298 K)


S39




(m, 2H, o-Ph), 2.88 (d, 3JHH = 7.5 Hz, 2H, CH2N), 2.62 (s, 3H, CH3N), 1.87 (m, 1H,

CH2CH), 1.50 (m, 10H, C8H15), 1.36 (m, 2H, C8H15), 1.13 (m, 2H, C8H15).

13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 150.3 (i-Ph), 129.5 (m-Ph), 116.5 (p-

Ph), 112.6 (o-Ph), 60.0 (CH2N), 39.1 (CH3N), 36.8 (NCH2CH), 30.1 (C8H15), 27.6

(C8H15), 26.5 (C8H15), 25.7 (C8H15).


7.26 / 6.78, 6.69 (m-Ph / p-Ph, o-Ph), 2.88 / 1.87 (CH2N / CH2CH).


Ph), 6.78 / 116.5 ( p-Ph), 6.69 / 112.6 (o-Ph), 2.88 / 60.0 (CH2N), 2.62 / 39.1 (CH3N),

1.87 / 36.8 (NCH2CH), 1.50 / 30.0, 27.9, 26.5, 25.7 (C8H15), 1.13 / 30.1 (C8H15).



Ph, m-Ph), 2.88 / 26.5, 30.1, 36.8, 39.1, 150.3 (CH2N / C8H15, C8H15, NCH2CH,

CH3N, i-Ph).

S40

Fig S40. 1H NMR (400 MHz, C6D6, 298 K)


S41




(m, 2H, o-Ph), 2.87 (m, 1H, CH2N), 2.79 (m, 1H, CH2N), 2.63 (s, 3H, CH3N), 2.09

(br, 1H, C7H11), 2.01 (br, 1H, C7H11), 1.74 (m, 1H, CH2CH), 1.36 (m, 2H, C7H11),

1.19 (m, 2H, C7H11), 0.99 (m, 3H, C7H11), 0.88 (m, 1H, C7H11).


112.7 (o-Ph), 58.1 (CH2N), 41.2 (NCH2CH), 39.5 (C7H11), 38.9 (CH3N), 36.9 (C7H11),

35.5 (C7H11), 35.4 (C7H11), 30.2 (C7H11), 29.3 (C7H11).


7.26 / 6.78, 6.71 (m-Ph / p-Ph, o-Ph), 2.83 / 1.74 (CH2N / CH2CH).


Ph), 6.78 / 116.5 ( p-Ph), 6.71 / 112.7 (o-Ph), 2.87 / 58.1 (CH2N), 2.79 / 58.1 (CH2N),

2.63 / 38.9 (CH3N), 2.09 / 36.9 (C7H11), 2.01 / 39.5 (C7H11), 1.74 / 41.2 (NCH2CH),

1.36 / 30.2, 29.3 (C7H11,C7H11), 1.19 / 35.4, 35.5 (C7H11, C7H11), 0.99 / 35.4, 35.5,

30.2 (C7H11, C7H11, C7H11), 0.88 / 35.4, 35.5 (C7H11, C7H11).



Ph, m-Ph), 2.87 / 150.3, 38.9, 41.2, 35.5, 35.4 (NCH2CH / i-Ph, CH3N, NCH2CH,

C7H11, C7H11).

S42

Fig S42.1H NMR (400 MHz, C6D6, 298 K)


S43




(m, 2H, m-PhN), 7.02 (m, 2H, o-Ph), 6.58 (m, 2H, o-PhN), 3.00 (m, 2H, CH2N), 2.54

(s, 3H, CH3N), 2.45 (m, 1H, CHCH3), 2.23 (s, 3H, CH3), 1.67 (m, 2H, NCH2CH2),

1.08 (d, 3JHH = 7.0 Hz, 3H, CHCH3).



(CH2N), 38.3 (CH3N), 38.2 (CHCH3), 34.6 (NCH2CH2), 23.0 (CHCH3), 20.5 (CH3).


7.18 / 7.10, 7.02 (m-Ph / p-Ph, o-Ph), 7.06 / 6.58 (m-PhN / o-PhN), 2.45 / 1.67, 1.08



Ph), 7.10 / 126.4 (p-Ph), 7.06 / 130.1 (m-PhN), 7.02 / 127.3 (o-Ph), 6.58 / 113.3 (o-

PhN), 3.00 / 51.5 (CH2N), 2.54 / 38.3 (CH3N), 2.45 / 38.2 (CHCH3), 2.23 / 20.5

(CH3), 1.67 / 34.6 (NCH2CH2), 1.08 / 23.0 (CHCH3).


= 7.10 / 148.5, 130.0 (m-Ph / i-Ph, m-Ph), 7.06 / 147.9, 130.1, 20.5 (m-PhN / i-PhN,

m-PhN, CH3), 6.58 / 125.4, 113.3 (o-PhN / p-PhN, o-PhN), 3.00 / 147.9, 38.3, 38.2,

34.6 (CH2N / i-PhN, CH3N, CHCH3, NCH2CH2).

S44

Fig S44. 1H NMR (400 MHz, C6D6, 298 K)

S45




1H NMR (400 MHz, C6D6, 298 K): δ = 7.13 (m, 3H, m-Ph, m-PhN), 7.06 (m, 1H, p-

Ph), 6.98 (m, 2H, o-Ph), 6.57 (m, 1H, p-PhN), 6.42 (m, 1H, o-PhN), 6.40 (m, 1H, o-

PhN), 2.97 (m, 2H, CH2N), 2.52 (s, 3H, CH3N), 2.40 (m, 1H, CHCH3), 2.21 (s, 3H,

CH3), 1.64 (m, 2H, NCH2CH2), 1.04 (d, 3JHH = 7.0 Hz, 3H, CHCH3).


Ph), 129.4 (m-PhN), 128.8 (m-PhN), 127.3 (o-Ph), 126.5 (p-Ph), 117.6 (p-PhN),

113.6 (o-PhN), 110.2 (o-PhN), 51.2 (CH2N), 38.2 (CH3N), 38.1 (CHCH3), 34.6

(NCH2CH2), 23.1 (CHCH3), 22.2 (CH3).


7.13 / 7.06, 6.98, 6.57, 6.42 (m-Ph, m-PhN / p-Ph, o-Ph, p-PhN, o-PhN), 2.40 / 1.64,

1.04 (CHCH3 / NCH2CH2, CHCH3).


128.8 (m-PhN, m-PhN), 7.06 / 126.5 (p-Ph), 6.98 / 127.3 (o-Ph), 6.57 / 117.6 (p-PhN),

6.42 / 110.2 (o-PhN), 6.40 / 113.6 (o-PhN), 2.97 / 51.2 (CH2N), 2.52 / 38.2 (CH3N),

2.40 / 38.1 (CHCH3), 2.21 / 22.2 (CH3), 1.64 / 34.6 (NCH2CH2), 1.04 / 23.1 (CHCH3).


= 7.13 / 149.7, 147.1, 138.7, 113.6, 110.2 (m-PhN / i-PhN, i-Ph, m-Ph, o-PhN, o-

PhN), 2.97 / 149.7, 38.2, 38.1, 34.6 (CH2N / i-PhN, CH3N, CHCH3, NCH2CH2).

S46

Fig S46. 1H NMR (400 MHz, C6D6, 298 K)

S47




1H NMR (400 MHz, C6D6, 298 K): δ = 7.60 (m, 2H, 2-C6H5), 7.55 (m, 2H, m-PhN),

7.28 (m, 2H, 3-C6H5), 7.19 (m, 2H, m-Ph), 7.12 (m, 1H, 4-C6H5), 7.10 (m, 1H, p-Ph),

7.02 (m, 2H, o-Ph), 6.59 (m, 2H, o-PhN), 3.00 (m, 2H, NCH2), 2.54 (s, 3H, CH3N),

2.45 (m, 1H, CHCH3), 1.66 (m, 2H, NCH2CH2), 1.09 (d, 3H, 3JHH = 7.0 Hz, CHCH3).

13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 149.0 (i-PhN), 147.0 (i-Ph), 142.0 (1-

C6H5), 129.5 (p-PhN), 129.1 (3-C6H5), 128.8 (m-Ph), 128.2 (m-PhN), 127.3 (o-Ph),

126.6 (2-C6H5), 126.5 (p-Ph), 126.2 (4-C6H5), 113.0 (o-PhN), 51.1 (NCH2), 38.2

(CHCH3), 38.0 (CH3N), 34.6 (NCH2CH2), 23.0 (CHCH3).


7.60 / 7.28 (2-C6H5 / 3-C6H5), 7.55 / 6.59 (m-PhN / o-PhN), 7.19 / 7.10, 7.02 (m-PhN

/ p-Ph, o-Ph), 2.45 / 1.66, 1.09 (CHCH3 / NCH2CH2, CHCH3).


C6H5), 7.55 / 128.2 (m-PhN), 7.28 / 129.1 (3-C6H5), 7.19 / 128.8 (m-Ph), 7.12 / 126.2

(4-C6H5), 7.10 / 126.5 (p-Ph), 7.02 / 127.3 (o-Ph), 6.59 / 113.0 (o-PhN), 3.00 / 51.1

(NCH2), 2.54 / 38.0 (CH3N), 2.45 / 38.2 (CHCH3), 1.66 / 34.6 (NCH2CH2), 1.09 /

23.0 (CHCH3).


= 7.60 / 129.5, 126.2 (2-C6H5 / p-PhN, 4-C6H5), 7.55 / 149.0, 142.0, 128.2, 113.0 (m-

PhN / i-PhN, 1-C6H5, m-PhN, o-PhN), 7.19 / 147.0, 128.8 (m-Ph / i-Ph, m-Ph), 3.00 /

149.0, 38.2, 38.0, 34.6 (NCH2 / i-PhN, CHCH3, CH3N, NCH2CH2).

S48

Fig S48. 1H NMR (400 MHz, C6D6, 298 K)

S49




1H NMR (400 MHz, C6D6, 298 K): δ = 7.70 (m, 2H, 8-C6H5), 7.35 (m, 3H, 4-C6H4,

9-C6H5), 7.26 (m, 3H, 10-C6H5, m-Ph), 7.20 (m, 1H, p-Ph), 7.11 (m, 3H, 6-C6H4, o-

Ph), 6.97 (m, 1H, 2-C6H4), 6.67 (m, 1H, 3-C6H4), 3.10 (m, 2H, NCH2), 2.65 (s, 3H,

CH3N), 2.52 (m, 1H, CHCH3), 1.75 (m, 2H, NCH2CH2), 1.16 (d, 3H, 3JHH = 7.0 Hz,

CHCH3).

13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 150.0 (1-C6H4), 147.0 (i-Ph), 143.1 (7-

C6H5), 142.8 (5-C6H4), 129.9 (9-C6H4), 129.0 (m-Ph), 128.9 (10-C6H5), 127.7 (8-

C6H5), 127.3 (o-Ph), 127.2 (4-C6H4), 126.5 (p-Ph), 115.8 (6-C6H4), 111.8 (2-C6H4),

111.7 (3-C6H4), 51.2 (NCH2), 38.2 (CHCH3), 38.1 (CH3N), 34.6 (NCH2CH2), 23.1

(CHCH3).


7.70 / 7.35 (8-C6H5 / 4-C6H4, 9-C6H5), 7.26 / 7.20, 7.11 (10-C6H5, m-Ph / p-Ph, 6-

C6H4, o-Ph), 6.67 / 7.36, 6.97 (3-C6H4 / 4-C6H4, 9-C6H5, 2-C6H4), 2.52 / 1.75, 1.16



C6H5), 7.35 / 129.9, 127.2 (9-C6H5, 4-C6H4), 7.26 / 129.0, 128.9 (10-C6H5, m-Ph),

7.20 / 126.5 (p-Ph), 7.11 / 127.3, 115.8 (o-Ph, 6-C6H4), 6.97 / 111.8 (2-C6H4), 6.67 /

111.7 (3-C6H4), 3.10 / 51.2 (NCH2), 2.65 / 38.1 (CH3N), 2.52 / 38.2 (CHCH3), 1.75 /

34.6 (NCH2CH2), 1.16 / 23.1 (CHCH3).


= 7.11 / 126.5, 38.2 (o-Ph / p-Ph, CHCH3), 6.67 / 142.8, 111.8, 115.8 (3-C6H4 / 5-

C6H4, 6-C6H4), 3.10 / 150.0, 38.2, 38.1, 34.6 (NCH2 / i-PhN, CHCH3, CH3N,

NCH2CH2).

S50

Fig S50. 1H NMR (400 MHz, C6D6, 298 K)

S51




1H NMR (400 MHz, C6D6, 298 K): δ = 7.21 (m, 2H, m-Ph), 7.18 (m, 1H, m-PhN),

7.12 (m, 1H, p-Ph), 7.07 (m, 2H, o-Ph), 6.62 (m, 1H, o-PhN), 6.57 (m, 1H, o-PhN),

3.06 (m, 2H, CH2N), 2.83 (t, 3JHH = 7.4 Hz, 4H, C3H6), 2.62 (s, 3H, CH3N), 2.50 (m,

1H, CHCH3), 1.94 (m, 2H, C3H6), 1.75 (m, 2H, NCH2CH2), 1.12 (d, 3JHH = 7.0 Hz,

3H, CHCH3).


PhN), 132.1 (p-PhN), 128.8 (m-Ph), 127.3 (o-Ph), 126.4 (p-Ph), 125.0 (m-PhN),

111.8 (o-PhN), 109.5 (o-PhN), 51.8 (NCH2), 38.7 (CH3N), 38.2 (CHCH3), 34.7

(NCH2CH2), 33.8 (C3H6), 32.4 (C3H6), 26.3 (C3H6), 23.0 (CHCH3).


7.21 / 7.12, 7.07 (m-Ph / p-Ph, o-Ph), 7.18 / 6.57 (m-PhN / o-PhN), 2.50 / 1.75, 1.12



Ph), 7.18 / 125.0 (m-PhN), 7.12 / 126.4 (p-Ph), 7.07 / 127.3 (o-Ph), 6.62 / 109.5 (o-

PhN), 6.57 / 111.8 (o-PhN), 3.06 / 51.8 (NCH2), 2.83 / 33.8, 32.4 (C3H6, C3H6), 2.62 /

38.7 (CH3N), 2.50 / 38.2 (CHCH3), 1.94 / 26.3 (C3H6), 1.75 / 34.7 (NCH2CH2), 1.12 /

23.0 (CHCH3).


= 7.21 / 147.2, 128.8 (i-Ph, m-Ph), 7.18 / 149.1, 145.3, 32.4 (i-PhN, m-PhN, C3H6),

3.06 / 149.1, 38.7, 38.2, 34.7 (CH2N / i-PhN, CH3N, CHCH3, NCH2CH2).

S52

Fig S52. 1H NMR (400 MHz, C6D6, 298 K)


S53

7f was isolated as pale yellow oil (133 mg, 85% yield).


1H NMR (400 MHz, C6D6, 298 K): δ = 7.66 (m, 2H, 5-C10H7, 8-C10H7), 7.58 (m, 1H,

3-C10H7), 7.33 (m, 1H, 7-C10H7), 7.18 (m, 3H, 6-C10H7, m-Ph), 7.11 (m, 1H, p-Ph),

7.00 (m, 2H, o-Ph), 6.89 (m, 1H, 2-C10H7), 6.80 (m, 1H, 10-C10H7), 3.00 (m, 2H,

NCH2), 2.56 (s, 3H, NCH3), 2.42 (m, 1H, CHCH3), 1.63 (m, 2H, NCH2CH2), 1.07 (d,

3H, 3JHH = 7.0 Hz, CHCH3).

13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 147.5 (1-C10H7), 147.0 (i-Ph), 136.0 (9-

C10H7), 129.1 (3-C10H7), 128.8 (m-Ph), 128.0 (overlapped with solvent, 5-C10H7, 8-

C10H7), 127.4 (4-C10H7), 127.3 (o-Ph), 126.6 (p-Ph), 126.5 (7-C10H7), 122.2 (6-C10H7),

116.4 (2-C10H7), 106.6 (10-C10H7), 51.2 (NCH2), 38.2 (NCH3), 38.1 (CHCH3), 34.7

(NCH2CH2), 23.0 (CHCH3).


7.58 / 6.89 (3-C10H7 / 2-C10H7), 7.18 / 7.66, 7.36, 7.11, 7.00 (6-C10H7, m-Ph / 5-C10H7,

8-C10H7, 7-C10H7, p-Ph, o-Ph), 2.42 / 1.63, 1.07 (CHCH3 / NCH2CH2, CHCH3).


C10H7, 8-C10H7), 7.58 / 129.1 (3-C10H7), 7.33 / 126.5 (7-C10H7), 7.18 / 128.8, 122.2

(m-Ph, 6-C10H7), 7.11 / 126.6 (p-Ph), 7.00 / 127.3 (o-Ph), 6.89 / 116.4 (2-C10H7), 6.80

/ 106.6 (10-C10H7), 3.00 / 51.2 (NCH2), 2.56 / 38.2 (NCH3), 2.42 / 38.1 (CHCH3),

1.63 / 34.7 (NCH2CH2), 1.07 / 23.0 (CHCH3).


= 7.66 / 136.0, 127.4, 122.2, 106.6 (5-C10H7, 8-C10H7 / 9-C10H7, 4-C10H7, 6-C10H7,

10-C10H7), 7.18 / 147.0, 128.0 (6-C10H7, m-Ph / i-Ph, 5-C10H7, 8-C10H7), 3.00 / 147.5,

38.2, 38.1 (NCH2 / 1-C10H7, NCH3, CHCH3).

S54

Fig S54. 1H NMR (400 MHz, C6D6, 298 K)


S55

7g was isolated as pale yellow oil (99 mg, 65% yield).


1H NMR (400 MHz, C6D6, 298 K): δ = 7.13 (m, 2H, o-Ph), 7.05 (m, 1H, p-Ph), 7.02

(m, 2H, m-Ph), 6.71 (m, 2H, 3-C6H4), 6.66 (m, 2H, 2-C6H4), 2.98 (m, 2H, NCH2),

2.58 (s, 6H, NMe2), 2.57 (s, 3H, CH3N), 2.52 (m, 1H, CHCH3), 1.69 (m, 2H,

NCH2CH2), 1.07 (d, 3H, 3JHH = 7.0 Hz, CHCH3).

13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 147.4 (i-Ph), 144.2 (1-C6H4), 143.1 (4-

C6H4), 128.8 (m-Ph), 127.3 (o-Ph), 126.4 (p-Ph), 115.8 (2-C6H4), 115.7 (3-C6H4),

52.7 (NCH2), 41.9 (NMe2), 39.2 (NCH3), 38.2 (CHCH3), 34.8 (NCH2CH2), 23.0

(CHCH3).


7.13 / 7.05, 7.02 (m-Ph / p-Ph, m-Ph), 6.71 / 6.66 (3-C6H4 / 2-C6H4), 2.52 / 1.69, 1.07



Ph), 7.05 / 126.4 (p-Ph), 7.02 / 127.3 (o-Ph), 6.71 / 115.7 (3-C6H4), 6.66 / 115.8 (2-

C6H4), 2.98 / 52.7 (NCH2), 2.58 / 41.9 (NMe2), 2.57 / 39.2 (NCH3), 2.52 / 38.2

(CHCH3), 1.69 / 34.8 (NCH2CH2), 1.07 / 23.0 (CHCH3).


= 7.13 / 147.4, 128.8, 127.3 (o-Ph / i-Ph, m-Ph, o-Ph), 6.71 / 144.2, 115.8, 115.7 (3-

C6H4 / 1-C6H4, 2-C6H4, 3-C6H4), 2.98 / 143.1, 39.2, 38.2 (NCH2 / 4-C6H4, NCH3,

CHCH3).

S56

Fig S56. 1H NMR (400 MHz, C6D6, 298 K)


S57

8 was isolated as pale yellow oil (38 mg, 30% yield).

1H NMR (400 MHz, CDCl3, 298 K): δ = 7.22 (m, 2H, m-Ph), 6.67 (m, 3H, o-Ph, p-

Ph), 3.22 (dd, 2JHH = 14.5 Hz, 3JHH = 6.6 Hz, 1H, NCH2), 3.02 (dd, 2JHH = 14.5 Hz,

3JHH = 8.1 Hz, 1H, NCH2), 2.95 (s, 3H, NCH3), 1.91 (m, 1H, C5H10), 1.40 (m, 1H,

C5H10), 1.28 (m, 8H, C5H10), 1.11 (m, 1H, CHCH3), 0.89 (m, 6H, CHCH3, CH2CH3).

13C{1H} NMR (101 MHz, CDCl3, 298 K): δ = 149.9 (i-Ph), 129.2 (m-Ph), 115.7 (p-

Ph), 111.9 (o-Ph), 60.0 (NCH2), 39.6 (NCH3), 34.9 (CHCH3), 32.4 (C5H10), 32.0

(C5H10), 29.8 (C5H10), 27.2 (C5H10), 22.8 (C5H10), 17.9 (CHCH3), 14.3 (CH2CH3).

Fig S58. 1H NMR (400 MHz, CDCl3, 298 K)

S58

Fig S59. 13C{1H} NMR (101 MHz, CDCl3, 298 K)

9 was isolated as pale yellow oil (76 mg, 60% yield).

1H NMR (400 MHz, CDCl3, 298 K): δ = 7.22 (m, 1H, 2-C6H4), 7.16 (m, 2H, 1-C6H4,

4-C6H4), 7.07 (m, 1H, 3-C6H4), 3.40 (m, 1H, CHCH3), 2.67 (s, 6H, NMe2), 1.54 (m,

2H, CHCH2), 1.22 (m, 11H, CHCH3, C4H8), 0.87 (t, 3JHH = 6.6 Hz, 3H, CH2CH3).

13C{1H} NMR (101 MHz, CDCl3, 298 K): δ = 152.5 (i-Ph), 143.7 (o-Ph), 126.8 (2-

C6H4), 126.2 (4-C6H4), 124.1 (3-C6H4), 119.8 (1-C6H4), 45.9 (C4H8), 38.7 (CHCH2),

32.0 (C4H8), 31.8 (CHCH3), 29.6 (C4H8), 27.9 (C4H8), 22.9 (C4H8), 22.4 (CHCH3),

14.3 (CH2CH3).

S59

Fig S60. 1H NMR (400 MHz, CDCl3, 298 K)

Fig S61. 13C{1H} NMR (101 MHz, CDCl3, 298 K)

S60

Deuterium labeling experiment:

Scheme S2.

Complex 1 (60 mg, 0.108 mmol) was added to a solution of [PhNHMe2][B(C6F5)4]

(87 mg, 0.108 mmol) in 1.0 mL of toluene. After stirring at room temperature for 1h,

amine (0.81 mmol) and alkene (0.54 mmol) were added and the reaction mixture was

heated and maintained at 120oC. After completion of the reaction (monitored by 1H

NMR), the mixture was cooled to room temperature and the volatiles were removed

under vacuum. The residue was purified by silica gel column chromatography to

afford alkylation product 7a-d6.

Fig S62. 1H NMR (400 MHz, C6D6, 298 K)

hydroaminoalkylation of sterically hindered alkenes with n,n · s1 hydroaminoalkylation of...

Documents