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
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).
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
Fig S5. 13C{1H} NMR (101 MHz, C6D6, 298 K)
4b was isolated as pale yellow oil (117 mg, 85% yield).
HRMS (ESI) m/z calcd. For C18H24N [M + H]+: 254.1903; found: 254.1917.
1H NMR (400 MHz, C6D6, 298 K): δ = 7.24 (m, 2H, m-PhN), 7.03 (m, 2H, m-Ph),
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,
NCH2CH2), 1.10 (d, 3JHH = 6.9 Hz, 3H, CHCH3).
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).
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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
Fig S7. 13C{1H} NMR (101 MHz, C6D6, 298 K)
4c was isolated as pale yellow oil (146 mg, 86% yield).
HRMS (ESI) m/z calcd. For C23H26N [M + H]+: 316.2060; found: 316.2075.
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
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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
Fig S9. 13C{1H} NMR (101 MHz, C6D6, 298 K)
4d was isolated as pale yellow oil (122 mg, 81% yield).
HRMS (ESI) m/z calcd. For C20H26N [M + H]+: 280.2060; found: 280.2072.
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
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.37 / 126.1 (m-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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
Fig S11. 13C{1H} NMR (101 MHz, C6D6, 298 K)
4e was isolated as pale yellow oil (142 mg, 91% yield).
HRMS (ESI) m/z calcd. For C21H24N [M + H]+: 290.1903; found: 290.1906.
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
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.65 / 128.6,
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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
Fig S13. 13C{1H} NMR (101 MHz, C6D6, 298 K)
4f was isolated as pale yellow oil (117 mg, 86 % yield).
HRMS (ESI) m/z calcd. For C18H24N [M + H]+: 254.1903; found: 254.1920.
1H NMR (400 MHz, C6D6, 298 K): δ = 7.24 (m, 2H, m-PhN), 7.14 (m, 1H, m-Ph),
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,
NCH2CH2), 1.10 (d, 3JHH = 7.0 Hz, 3H, CHCH3).
13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 149.7 (i-PhN), 147.1 (i-Ph), 138.0 (m-
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
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.24 / 129.5 (m-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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
Fig S15. 13C{1H} NMR (101 MHz, C6D6, 298 K)
4g was isolated as pale yellow oil (117 mg, 78 % yield).
HRMS (ESI) m/z calcd. For C20H26N [M + H]+: 280.2060; found: 280.2078.
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
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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
Fig S17. 13C{1H} NMR (101 MHz, C6D6, 298 K)
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.
1H NMR (400 MHz, C6D6, 298 K): δ = 7.22 (m, 4H, m-PhN), 7.18 (m, 1H, m-Ph),
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,
NCH2CH2), 1.13 (d, 3JHH = 6.9 Hz, 6H, CHCH3).
13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 149.7 (i-PhN), 147.4 (i-Ph), 129.5 (m-
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).
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.22 / 129.5 (m-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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
Fig S19. 13C{1H} NMR (101 MHz, C6D6, 298 K)
4i was isolated as pale yellow oil (168 mg, 78% yield).
HRMS (ESI) m/z calcd. For C28H37N2 [M + H]+: 401.2951; found: 401.2960.
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).
13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 149.7 (i-PhN), 144.9 (i-Ph), 129.5 (m-
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).
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
7.24 / 6.77, 6.61 (m-PhN / p-PhN, o-PhN), 2.48 / 1.70, 1.12 (CHCH3 / NCH2CH2,
CHCH3).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.24 / 129.5 (m-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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
Fig S21. 13C{1H} NMR (101 MHz, C6D6, 298 K)
4j was isolated as pale yellow oil (102 mg, 75% yield).
HRMS (ESI) m/z calcd. For C18H24N [M + H]+: 254.1903; found: 254.1918.
1H NMR (400 MHz, C6D6, 298 K): δ = 7.19 (m, 2H, m-PhN), 7.12 (m, 2H, m-Ph),
7.05 (m, 1H, p-Ph), 6.94 (m, 2H, o-Ph), 6.73 (m, 1H, p-PhN), 6.53 (m, 2H, o-PhN),
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).
13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 149.7 (i-PhN), 145.2 (i-Ph), 129.5 (m-
PhN), 128.7 (m-Ph), 128.0 (o-Ph), 126.5 (p-Ph), 116.5 (p-PhN), 112.7 (o-PhN), 51.2
(CH2N), 45.9 (CHCH2CH3), 38.0 (CH3N), 33.0 (NCH2CH2), 30.3 (CHCH2CH3), 12.3
(CHCH2CH3).
S23
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
7.19 / 6.73, 6.53 (m-PhN / p-PhN, o-PhN), 7.12 / 7.05, 6.94 (m-Ph / p-Ph, o-Ph), 1.71
/ 2.94, 2.16 (NCH2CH2 / CH2N, CHCH2CH3), 1.40 / 2.16, 0.66 (CHCH2CH3 /
CHCH2CH3, CHCH2CH3).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.19 / 129.5 (m-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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
Fig S23. 13C{1H} NMR (101 MHz, C6D6, 298 K)
4k was isolated as pale yellow oil (91 mg, 63% yield).
HRMS (ESI) m/z calcd. For C19H26N [M + H]+: 268.2060; found: 268.2075.
1H NMR (400 MHz, C6D6, 298 K): δ = 7.23 (m, 2H, m-PhN), 7.18 (m, 2H, m-Ph),
7.09 (m, 1H, p-Ph), 7.01 (m, 2H, o-Ph), 6.77 (m, 1H, p-PhN), 6.58 (m, 2H, o-PhN),
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-
PhN), 128.7 (m-Ph), 128.0 (o-Ph), 126.5 (p-Ph), 116.6 (p-PhN), 112.8 (o-PhN), 51.2
(CH2N), 43.9 (CHCH2CH2CH3), 39.8 (CHCH2CH2CH3), 38.1 (CH3N),
33.3(NCHCH2), 21.0 (CHCH2CH2CH3), 14.3 (CHCH2CH2CH3).
S25
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
7.23 / 6.77, 6.59 (m-PhN / p-PhN, o-PhN), 7.18 / 7.09, 7.01 (m-Ph / p-Ph, o-Ph), 1.76
/ 2.99, 2.33 (NCH2CH2 / CH2N, CHCH2CH2CH3), 1.40 / 2.33, 1.08 (CHCH2CH2CH3 /
CHCH2CH2CH3, CHCH2CH2CH3).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.23 / 129.5 (m-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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
Fig S25. 13C{1H} NMR (101 MHz, C6D6, 298 K)
4l was isolated as pale yellow oil (83 mg, 58% yield).
HRMS (ESI) m/z calcd. For C19H24N [M + H]+: 266.1903; found: 266.1912.
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
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.26 / 129.5 (m-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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
Fig S27. 13C{1H} NMR (101 MHz, C6D6, 298 K)
4m was isolated as pale yellow oil (122 mg, 75% yield).
HRMS (ESI) m/z calcd. For C22H24N [M + H]+: 302.1903; found: 302.1916.
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).
13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 149.6 (i-PhN), 145.0 (i-Ph), 129.5 (m-
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).
S30
Fig S29. 13C{1H} NMR (101 MHz, C6D6, 298 K)
5a was isolated as pale yellow oil (58 mg, 53% yield).
HRMS (ESI) m/z calcd. For C14H22N [M + H]+: 204.1747; found: 204.1759.
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).
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
7.25 / 6.78, 6.73 (m-Ph / p-Ph, o-Ph), 3.01 / 2.65 (CH2N / CH3N).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.25 / 129.3 (m-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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).
S32
Fig S31. 13C{1H} NMR (101 MHz, C6D6, 298 K)
5b was isolated as pale yellow oil (68 mg, 58% yield).
HRMS (ESI) m/z calcd. For C15H24N [M + H]+: 218.1903; found: 218.1902.
1H NMR (400 MHz, C6D6, 298 K): δ = 7.26 (m, 2H, m-Ph), 6.78 (m, 1H, p-Ph), 6.74
(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).
13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 151.3 (i-Ph), 129.2 (m-Ph), 116.4 (p-Ph),
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).
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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).
S34
6a was isolated as pale yellow oil (72 mg, 65% yield).
HRMS (ESI) m/z calcd. For C14H24N [M + H]+: 206.1903; found: 206.1915.
1H NMR (400 MHz, C6D6, 298 K): δ = 7.26 (m, 2H, m-Ph), 6.78 (m, 1H, p-Ph), 6.69
(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).
13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 150.3 (i-Ph), 129.5 (m-Ph), 116.5 (p-Ph),
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).
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.26 / 129.5 (m-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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).
S36
6b was isolated as pale yellow oil (53 mg, 52% yield).
HRMS (ESI) m/z calcd. For C13H20N [M + H]+: 190.1590; found: 190.1598.
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).
13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 150.1 (i-Ph), 129.5 (m-Ph), 116.5 (p-Ph),
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
Fig S37. 13C{1H} NMR (101 MHz, C6D6, 298 K)
6c was isolated as pale yellow oil (69 mg, 63% yield).
HRMS (ESI) m/z calcd. For C14H22N [M + H]+: 204.1747; found: 204.1756.
1H NMR (400 MHz, C6D6, 298 K): δ = 7.27 (m, 2H, m-Ph), 6.78 (m, 1H, p-Ph), 6.67
(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).
13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 150.1 (i-Ph), 129.5 (m-Ph), 116.3 (p-Ph),
112.4 (o-Ph), 59.8 (CH2N), 39.4 (CH3N), 37.1 (C6H11), 31.5 (C6H11), 26.9 (C6H11),
26.4 (C6H11).
S39
6d was isolated as pale yellow oil (89 mg, 71% yield).
HRMS (ESI) m/z calcd. For C16H26N [M + H]+: 232.2060; found: 232.2061.
1H NMR (400 MHz, C6D6, 298 K): δ = 7.26 (m, 2H, m-Ph), 6.78 (m, 1H, p-Ph), 6.69
(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).
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
7.26 / 6.78, 6.69 (m-Ph / p-Ph, o-Ph), 2.88 / 1.87 (CH2N / CH2CH).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.26 / 129.5 (m-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 7.26 / 112.6, 129.5, 150.3 (m-Ph / o-Ph, m-Ph, i-Ph), 6.78 / 112.6, 129.5 ( p-Ph / o-
Ph, m-Ph), 2.88 / 26.5, 30.1, 36.8, 39.1, 150.3 (CH2N / C8H15, C8H15, NCH2CH,
CH3N, i-Ph).
S41
6e was isolated as pale yellow oil (83 mg, 71% yield).
HRMS (ESI) m/z calcd. For C15H22N [M + H]+: 216.1747; found: 216.1762.
1H NMR (400 MHz, C6D6, 298 K): δ = 7.26 (m, 2H, m-Ph), 6.78 (m, 1H, p-Ph), 6.71
(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).
13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 150.3 (i-Ph), 129.5 (m-Ph), 116.5 (p-Ph),
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).
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
7.26 / 6.78, 6.71 (m-Ph / p-Ph, o-Ph), 2.83 / 1.74 (CH2N / CH2CH).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.26 / 129.5 (m-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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), 2.87 / 150.3, 38.9, 41.2, 35.5, 35.4 (NCH2CH / i-Ph, CH3N, NCH2CH,
C7H11, C7H11).
S43
7a was isolated as pale yellow oil (118 mg, 86% yield).
HRMS (ESI) m/z calcd. For C18H24N [M + H]+: 254.1903; found: 254.1905.
1H NMR (400 MHz, C6D6, 298 K): δ = 7.18 (m, 2H, m-Ph), 7.10 (m, 1H, p-Ph), 7.06
(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).
13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 147.9 (i-PhN), 147.2 (i-Ph), 130.1 (m-
PhN), 128.8 (m-Ph), 127.3 (o-Ph), 126.4 (p-Ph), 125.4 (p-PhN), 113.3 (o-PhN), 51.5
(CH2N), 38.3 (CH3N), 38.2 (CHCH3), 34.6 (NCH2CH2), 23.0 (CHCH3), 20.5 (CH3).
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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
(CHCH3 / NCH2CH2, CHCH3).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.18 / 128.8 (m-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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).
S45
Fig S45. 13C{1H} NMR (101 MHz, C6D6, 298 K)
7b was isolated as pale yellow oil (107 mg, 78% yield).
HRMS (ESI) m/z calcd. For C18H24N [M + H]+: 254.1903; found: 254.1907.
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).
13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 149.7 (i-PhN), 147.1 (i-Ph), 138.7 (m-
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).
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.13 / 129.4,
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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).
S47
Fig S47. 13C{1H} NMR (101 MHz, C6D6, 298 K)
7c was isolated as pale yellow oil (148 mg, 87% yield).
HRMS (ESI) m/z calcd. For C23H26N [M + H]+: 316.2060; found: 316.2056.
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).
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.60 / 126.6 (2-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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).
S49
Fig S49. 13C{1H} NMR (101 MHz, C6D6, 298 K)
7d was isolated as pale yellow oil (127 mg, 75% yield).
HRMS (ESI) m/z calcd. For C23H26N [M + H]+: 316.2060; found: 316.2052.
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).
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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
(CHCH3 / NCH2CH2, CHCH3).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.70 / 127.7 (8-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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).
S51
Fig S51. 13C{1H} NMR (101 MHz, C6D6, 298 K)
7e was isolated as pale yellow oil (122 mg, 81% yield).
HRMS (ESI) m/z calcd. For C20H26N [M + H]+: 280.2060; found: 280.2071.
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).
13C{1H} NMR (101 MHz, C6D6, 298 K): δ = 149.1 (i-PhN), 147.2 (i-Ph), 145.3 (m-
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).
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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
(CHCH3 / NCH2CH2, CHCH3).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.21 / 128.8 (m-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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).
S53
7f was isolated as pale yellow oil (133 mg, 85% yield).
HRMS (ESI) m/z calcd. For C21H24N [M + H]+: 290.1903; found: 290.1900.
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).
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.66 / 128.0 (5-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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).
S55
7g was isolated as pale yellow oil (99 mg, 65% yield).
HRMS (ESI) m/z calcd. For C19H27N2 [M + H]+: 283.2169; found: 283.2174.
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).
1H, 1H GCOSY (400 MHz / 400 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 1H =
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
(CHCH3 / NCH2CH2, CHCH3).
1H, 13C GHSQC (400 MHz / 101 MHz, C6D6, 298 K): δ 1H / δ 13C = 7.13 / 128.8 (m-
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).
1H, 13C GHMBC (400 MHz / 101 MHz, C6D6, 298 K) [selected traces]: δ 1H / δ 13C
= 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).
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).
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)