Exploring bis-(amino)cyclopropenylidene as a non-covalent Brønsted base catalyst in conjugate add

64 Pages·2017·10.18 MB·English

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
This journal is © The Royal Society of Chemistry 2017
Supporting Information for
“Exploring bis-(amino)cyclopropenylidene as a non-covalent Brønsted base catalyst in
conjugate addition reactions”

Gurdeep Singh, Prithwish Goswami and Ramasamy Vijaya Anand*
Indian Institute of Science Education and Research (IISER) Mohali, Sector 81, S. A. S.
Nagar, Manauli (PO). Punjab – 140306, India
E–mail: [email protected]

Table of Contents
1. General methods S2
2. General procedure for the 1,6-conjugate addition of active methylenes to p-QMs S2–S3
3. Characterisation of product 3a S3
4. Characterisation of products (3b to 3o) S3–S10
5. Characterisation of products (13a to 13d) S10–S12
6. General procedure for the 1,6-conjugate addition of 2-naphthols to p-QMs S12
7. Characterisation of products (15a to 15e) S12–S14
8. General procedure for the 1,4-conjugate addition of malonates to chalcones S15
9. Characterisation of products (17a to 17n) S15–S21
10. Synthetic elaboration of 13a S22
11. References S23
12. NMR spectra of products (3a to 3o) S24–S39
13. NMR spectra of products (13a to 13d) S39–S43
14. NMR spectra of products (15a to 15e) S43–S48
15. NMR spectra of products (17a to 17n) S48–S63
16. NMR spectra of product 18 S63–S64
S1
Experimental Section
1. General methods
All reactions were carried out under an argon atmosphere in an oven dried round bottom
flask. All the solvents were distilled before use and stored under argon atmosphere. Most of
the reagents, starting materials and NHC precursors (5 to 9) were purchased from commercial
sources and used as such. All p-quinone methides were prepared by following a literature
procedure.1 NHC precursor 4 was prepared according to the literature procedure.2 BAC
precursors 10, 11 and 12 were prepared according to known procedures.3 All chalcones were
prepared according to the known literature procedure.4 Melting points were recorded on
SMP20 melting point apparatus and are uncorrected. 1H, 13C and 19F spectra were recorded in
CDCl (400, 100 and 376 MHz respectively) on Bruker FT–NMR spectrometer. Chemical
3
shift (d) values are reported in parts per million relative to TMS and the coupling constants
(J) are reported in Hz. High resolution mass spectra were recorded on Waters Q–TOF
Premier–HAB213 spectrometer. FT-IR spectra were recorded on a Perkin-Elmer FTIR
spectrometer. Thin layer chromatography was performed on Merck silica gel 60 F TLC
254
pellets and visualised by UV irradiation and KMnO stain. Column chromatography was
4
carried out through silica gel (100–200 mesh) using EtOAc/hexane as an eluent.
2. General General procedure for the 1,6-conjugate addition of active methylene
compounds to p-quinone methides:
Anhydrous THF (1.0 mL) was added to the mixture of p-quinone methide (0.062 mmol),
diethyl malonate (0.074 mmol), catalyst 11 (0.0062 mmol) and Cs CO (0.0062 mmol) under
2 3
argon atmosphere and the resulting suspension was stirred at room temperature. After the
reaction was complete (based on TLC analysis), the reaction mixture was concentrated under
S2
reduced pressure. The residue was then purified through a silica gel column, using
EtOAc/Hexane mixture as an eluent, to get the pure product.
3. Characterisation of product 3a
Diethyl 2-((3,5-di-tert-butyl-4-hydroxyphenyl)(4-methoxyphenyl)methyl)malonate (3a)

The reaction was performed at 0.062 mmol scale of 1a; R = 0.4 (10%
f
EtOAc in hexane); pale yellow gummy solid (28.1 mg, 94% yield); 1H
NMR (400 MHz, CDCl ) δ 7.23 (d, J = 8.6 Hz, 2H), 7.05 (s, 2H), 6.80 (d,
3
J = 8.6 Hz, 2H), 5.03 (s, 1H), 4.59 (d, J = 12.2 Hz, 1H), 4.22 (d, J = 12.2 Hz, 1H), 4.03 –
3.92 (m, 4H), 3.75 (s, 3H), 1.38 (s, 18H), 1.04 (t, J = 7.1 Hz, 3H), 0.95 (t, J = 7.1 Hz, 3H);
13C NMR (100 MHz, CDCl ) δ 168.07, 168.06, 158.3, 152.6, 135.7, 134.3, 132.1, 128.9,
3
124.4, 114.0, 61.5, 61.4, 58.5, 55.3, 50.8, 34.4, 30.4, 14.0, 13.9; FT-IR (thin film, neat):
3442, 2958, 1758, 1732, 1612, 1513, 1436, 1303, 1250, 1179, 1036, 838, 637 cm-1; HRMS
(ESI): m/z calcd for C H O [M-H]+ : 483.2747; found : 483.2727.
29 39 6
4. Characterisation of products (3b to 3o)
Diethyl 2-((3,5-di-tert-butyl-4-hydroxyphenyl)(2,3-dimethoxyphenyl)methyl)malonate
(3b)
The reaction was performed at 0.0565 mmol scale of 1b; R = 0.3 (10%
f
EtOAc in hexane); brown solid (26.7 mg, 92% yield); m. p. = 100–104
ºC; 1H NMR (400 MHz, CDCl ) δ 7.10 (s, 2H), 7.01 – 6.94 (m, 2H), 6.75
3
(d, J = 7.8 Hz, 1H), 5.07 (d, J = 12.5 Hz, 1H), 4.99 (s, 1H), 4.35 (d, J = 12.5 Hz, 1H), 4.00 (q,
J = 7.1 Hz, 2H), 3.96 (q, J = 7.1 Hz, 2H), 3.80 (s, 3H), 3.74 (s, 3H), 1.37 (s, 18H), 1.03 (t, J =
7.1 Hz, 3H), 0.94 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl ) δ 168.3, 168.0, 153.1,
3
152.4, 147.0, 136.2, 135.4, 131.6, 124.9, 123.8, 119.0, 110.9, 61.4, 61.3, 60.4, 57.4, 55.7,
S3
44.6, 34.4, 30.4, 13.93, 13.89; FT-IR (thin film, neat): 3417, 2959, 1758, 1732, 1586, 1479,
1435, 1368, 1274, 1155, 1094, 1037, 862, 746 cm-1; HRMS (ESI): m/z calcd for C H NaO
30 42 7
[M+Na]+ : 537.2828; found : 537.2804.
Diethyl 2-((3,5-di-tert-butyl-4-hydroxyphenyl)(3,5-dimethoxyphenyl)methyl)malonate
(3c)
The reaction was performed at 0.0564 mmol scale of 1c; R = 0.3 (10%
f
EtOAc in hexane); pale yellow solid (26.4 mg, 91% yield); m. p. = 110–
114 ºC; 1H NMR (400 MHz, CDCl ) δ 7.08 (s, 2H), 6.48 (s, 2H), 6.27 (s,
3
1H), 5.05 (s, 1H), 4.56 (d, J = 12.2 Hz, 1H), 4.23 (d, J = 12.2 Hz, 1H), 4.04 (q, J = 7.1 Hz,
2H), 3.95 (q, J = 7.0 Hz, 2H), 3.75 (s, 6H), 1.39 (s, 18H), 1.07 (t, J = 7.1 Hz, 3H), 0.94 (t, J =
7.1 Hz, 3H); 13C NMR (100 MHz, CDCl ) δ 168.0, 167.9, 160.8, 152.8, 144.4, 135.7, 131.4,
3
124.5, 106.1, 98.7, 61.6, 61.4, 58.2, 55.4, 51.7, 34.5, 30.4, 14.00, 13.9; FT-IR (thin film,
neat): 3616, 3443, 2959, 1758, 1732, 1597, 1463, 1435, 1368, 1204, 1156, 1065, 1036, 847,
698 cm-1; HRMS (ESI): m/z calcd for C H NaO [M+Na]+ : 537.2828; found : 537.2806.
30 42 7
Diethyl 2-((3,5-di-tert-butyl-4-hydroxyphenyl)(3,4-dimethoxyphenyl)methyl)malonate
(3d)
The reaction was performed at 0.0564 mmol scale of 1d; R = 0.3 (10%
f
EtOAc in hexane); orange gummy solid (26.1 mg, 90% yield); 1H NMR
(400 MHz, CDCl ) δ 7.08 (s, 2H), 6.88 – 6.85 (m, 2H), 6.77 (d, J = 8.1
3
Hz, 1H), 5.04 (s, 1H), 4.58 (d, J = 12.1 Hz, 1H), 4.21 (d, J = 12.1 Hz, 1H), 4.04 – 3.93 (m,
4H), 3.85 (s, 3H), 3.82 (s, 3H), 1.39 (s, 18H), 1.05 (t, J = 7.1 Hz, 3H), 0.95 (t, J = 7.1 Hz,
3H); 13C NMR (100 MHz, CDCl ) δ 168.03, 168.00, 152.7, 148.8, 147.8, 135.8, 134.7, 131.9,
3
124.5, 119.8, 111.4, 111.3, 61.6, 61.4, 58.7, 56.0, 55.9, 51.2, 34.5, 30.4, 14.0, 13.9; FT-IR
(thin film, neat): 3458, 2959, 1758, 1732, 1592, 1515, 1464, 1436, 1367, 1262, 1143, 1030,
S4
858, 663 cm-1; HRMS (ESI): m/z calcd for C H NaO [M+Na]+ : 537.2828; found :
30 42 7
537.2804.
Diethyl 2-((3-(allyloxy)phenyl)(3,5-di-tert-butyl-4-hydroxyphenyl)methyl)malonate (3e)
The reaction was performed at 0.0571 mmol scale of 1e; R = 0.3 (10%
f
EtOAc in hexane); pale yellow gummy solid (26.8 mg, 92% yield); 1H NMR
(400 MHz, CDCl ) δ 7.32 (d, J = 7.4 Hz, 1H), 7.13 – 7.09 (m, 3H), 6.89 (t, J
3
= 7.4 Hz, 1H), 6.77 (d, J = 8.2 Hz, 1H), 6.08 – 5.99 (m, 1H), 5.37 (d, J = 17.3 Hz, 1H), 5.25
(d, J = 10.5 Hz, 1H), 5.06 (d, J = 12.4 Hz, 1H), 4.99 (s, 1H), 4.58 – 4.48 (m, 3H), 4.02 – 3.93
(m, 4H), 1.37 (s, 18H), 1.00 (t, J = 7.1 Hz, 3H), 0.94 (t, J = 7.1 Hz, 3H); 13C NMR (100
MHz, CDCl ) δ 168.5, 168.1, 156.0, 152.4, 135.3, 133.6, 131.5, 130.9, 127.7, 127.6, 125.1,
3
120.7, 117.3, 112.3, 69.0, 61.31, 61.27, 56.9, 45.4, 34.4, 30.4, 13.9 (2C); FT-IR (thin film,
neat): 3638, 3446, 2959, 1758, 1732, 1599, 1492, 1436, 1368, 1242, 1120, 1035, 929, 868,
752, 645 cm-1; HRMS (ESI): m/z calcd for C H NaO [M+Na]+ : 533.2879; found :
31 42 6
533.2856.
Diethyl 2-((3,5-di-tert-butyl-4-hydroxyphenyl)(phenyl)methyl)malonate (3f)
The reaction was performed at 0.0679 mmol scale of 1f; R = 0.2 (5%
f
EtOAc in hexane); white solid (29.02 mg, 94% yield); m. p. = 110–113 ºC;
1H NMR (400 MHz, CDCl ) δ 7.33 – 7.31 (m, 2H), 7.26 (s, 2H), 7.18 –
3
7.14 (m, 1H), 7.07 (s, 2H), 5.04 (s, 1H), 4.64 (d, J = 12.2 Hz, 1H), 4.27 (d, J = 12.2 Hz, 1H),
4.01 – 3.94 (m, 4H), 1.38 (s, 18H), 1.00 (t, J = 7.1 Hz, 3H), 0.95 (t, J = 7.1 Hz, 3H); 13C
NMR (100 MHz, CDCl ) δ 168.1, 168.0, 152.7, 142.1, 135.8, 131.7, 128.6, 127.9, 126.8,
3
124.5, 61.5, 61.4, 58.3, 51.6, 34.5, 30.4, 13.92, 13.90; FT-IR (thin film, neat): 3638, 3440,
2959, 1759, 1732, 1601, 1436, 1368, 1316, 1259, 1177, 1156, 1036, 865, 700, 645 cm-1;
HRMS (ESI): m/z calcd for C H NaO [M+Na]+ : 477.2617; found : 477.2636.
28 38 5

S5
Diethyl 2-((4-(tert-butyl)phenyl)(3,5-di-tert-butyl-4-hydroxyphenyl)methyl)malonate
(3g)
The reaction was performed at 0.0571 mmol scale of 1g; R = 0.3 (5%
f
EtOAc in hexane); pale yellow gummy solid (27.1 mg, 93% yield); 1H
NMR (400 MHz, CDCl ) δ 7.28 – 7.22 (m, 4H), 7.09 (s, 2H), 5.03 (s,
3
1H), 4.59 (d, J = 12.2 Hz, 1H), 4.25 (d, J = 12.2 Hz, 1H), 4.01 – 3.93 (m, 4H), 1.39 (s, 18H),
1.26 (s, 9H), 0.97 – 0.92 (m, 6H); 13C NMR (100 MHz, CDCl ) δ 168.11, 168.07, 152.6,
3
149.5, 138.9, 135.7, 131.9, 127.5, 125.5, 124.6, 61.42, 61.35, 58.5, 51.4, 34.48, 34.45, 31.5,
30.4, 13.88, 13.84; FT-IR (thin film, neat): 3443, 2961, 1760, 1732, 1596, 1436, 1367, 1314,
1257, 1176, 1156, 1037, 842, 630 cm-1; HRMS (ESI): m/z calcd for C H NaO [M+Na]+ :
32 46 5
533.3243; found : 533.3218.
Diethyl 2-((2-chlorophenyl)(3,5-di-tert-butyl-4-hydroxyphenyl)methyl)malonate (3h)
The reaction was performed at 0.061mmol scale of 1h; R = 0.2 (5%
f
EtOAc in hexane); pale yellow gummy solid (28.0 mg, 94% yield); 1H
NMR (400 MHz, CDCl ) δ 7.41 (d, J = 7.8 Hz, 1H), 7.32 (d, J = 7.9 Hz,
3
1H), 7.22 (t, J = 7.3 Hz, 1H), 7.13 (s, 2H), 7.12 – 7.08 (m, 1H), 5.24 (d, J = 12.4 Hz, 1H),
5.06 (s, 1H), 4.34 (d, J = 12.4 Hz, 1H), 4.06 – 3.94 (m, 4H), 1.38 (s, 18H), 1.02 (t, J = 7.1 Hz,
3H), 0.94 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl ) δ 167.8, 167.6, 152.8, 139.8,
3
135.7, 134.4, 130.2, 130.1, 127.8, 127.4, 127.0, 125.0, 61.7, 61.5, 57.9, 46.7, 34.4, 30.4,
13.90, 13.87; FT-IR (thin film, neat): 3638, 3451, 2960, 2927, 1758, 1732, 1592, 1436, 1368,
1257, 1157, 1037, 867, 753, 730, 643, 600 cm-1; HRMS (ESI): m/z calcd for C H ClNaO
28 37 5
[M+Na]+ : 511.2227; found : 511.2207.

S6
Diethyl 2-((2-bromophenyl)(3,5-di-tert-butyl-4-hydroxyphenyl)methyl)malonate (3i)
The reaction was performed at 0.0537 mmol scale of 1i; R = 0.2 (5%
f
EtOAc in hexane); white solid (26.6 mg, 93% yield); m. p. = 143–146 ºC;
1H NMR (400 MHz, CDCl ) δ 7.52 (d, J = 7.9 Hz, 1H), 7.40 (d, J = 7.7 Hz,
3
1H), 7.28 – 7.24 (m, 1H), 7.16 (s, 2H), 7.03 – 7.00 (m, 1H), 5.23 (d, J = 12.4 Hz, 1H), 5.06
(s, 1H), 4.33 (d, J = 12.3 Hz, 1H), 4.03 – 3.94 (m, 4H), 1.38 (s, 18H), 1.02 (t, J = 7.1 Hz,
3H), 0.94 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl ) δ 167.8, 167.6, 152.8, 141.4,
3
135.7, 133.6, 130.1, 128.1, 127.7, 127.5, 125.4, 125.0, 61.7, 61.5, 58.1, 49.1, 34.4, 30.4, 13.9
(2C); FT-IR (thin film, neat): 3635, 2959, 1758, 1732, 1590, 1468, 1436, 1368, 1255, 1156,
1035, 808, 753, 725, 642 cm-1; HRMS (ESI): m/z calcd for C H BrNaO [M+Na]+ :
28 37 5
555.1722; found : 555.1700.
Diethyl 2-((4-bromophenyl)(3,5-di-tert-butyl-4-hydroxyphenyl)methyl)malonate(3j)
The reaction was performed at 0.0537 mmol scale of 1j; R = 0.2 (5%
f
EtOAc in hexane); pale yellow gummy solid (26.3 mg, 92% yield); 1H
NMR (400 MHz, CDCl ) δ 7.39 (d, J = 8.4 Hz, 2H), 7.19 (d, J = 8.4 Hz,
3
2H), 7.02 (s, 2H), 5.07 (s, 1H), 4.61 (d, J = 12.2 Hz, 1H), 4.22 (d, J = 12.1 Hz, 1H), 4.04 –
3.94 (m, 4H), 1.38 (s, 18H), 1.06 (t, J = 7.1 Hz, 3H), 0.95 (t, J = 7.1 Hz, 3H); 13C NMR (100
MHz, CDCl ) δ 167.80, 167.78, 152.8, 141.3, 136.0, 131.7, 131.1, 129.6, 124.4, 120.6, 61.7,
3
61.5, 58.0, 50.9, 34.5, 30.4, 14.0, 13.9; FT-IR (thin film, neat): 3407, 2959, 1758, 1732,
1592, 1489, 1436, 1468, 1239, 1155, 1036, 1011, 811 cm-1; HRMS (ESI): m/z calcd for
C H BrNaO [M+Na]+ : 555.1722; found : 555.1700.
28 37 5
Diethyl 2-((3,5-di-tert-butyl-4-hydroxyphenyl)(2,4-dichlorophenyl)methyl)malonate (3k)
The reaction was performed at 0.055 mmol scale of 1k; R = 0.2 (5%
f
EtOAc in hexane); pale yellow gummy solid (27.4 mg, 95% yield); 1H
NMR (400 MHz, CDCl ) δ 7.35 (d, J = 2.0 Hz, 1H), 7.33 (d, J = 8.5, 1H),
3
S7
7.21 (dd, J = 8.4, 1.9 Hz, 1H), 7.09 (s, 2H), 5.18 (d, J = 12.4 Hz, 1H), 5.09 (s, 1H), 4.30 (d, J
= 12.4 Hz, 1H), 4.08 – 4.01 (m, 2H), 3.97 (q, J = 7.1 Hz, 2H), 1.38 (s, 18H), 1.07 (t, J = 7.1
Hz, 3H), 0.95 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz, CDCl ) δ 167.6, 167.4, 152.9, 138.6,
3
135.8, 135.1, 132.8, 130.0, 129.6, 128.2, 127.3, 124.8, 61.8, 61.6, 57.6, 46.2, 34.4, 30.4,
13.94, 13.90; FT-IR (thin film, neat): 3385, 2960, 2922, 1756, 1732, 1588, 1471, 1436, 1368,
1239, 1155, 1106, 1036, 867, 771 cm-1; HRMS (ESI): m/z calcd for C H Cl NaO [M+Na]+
28 36 2 5
: 545.1837; found : 545.1815.
Diethyl 2-((3,5-di-tert-butyl-4-hydroxyphenyl)(2,4-difluorophenyl)methyl)malonate (3l)
The reaction was performed at 0.0606 mmol scale of 1l; R = 0.3 (5%
f
EtOAc in hexane); white solid (27.0 mg, 91% yield); m. p. = 110–114 ºC;
1H NMR (400 MHz, CDCl ) δ 7.35 (t, J = 7.5 Hz, 1H), 7.13 (s, 2H), 7.06
3
(t, J = 7.4 Hz, 1H), 6.98 (t, J = 9.6 Hz, 1H), 5.07 (s, 1H), 4.93 (d, J = 12.4 Hz, 1H), 4.41 (d, J
= 12.4 Hz, 1H), 4.05 – 3.95 (m, 4H), 1.39 (s, 18H), 1.02 (t, J = 7.1 Hz, 3H), 0.96 (t, J = 7.1
Hz, 3H); 13C NMR (100 MHz, CDCl ) δ 167.9, 167.8, 160.6 (d, J = 244.7 Hz), 152.8,
3 C-F
135.7, 130.6, 129.4 (d, J = 14.0 Hz ), 128.7 (d, J = 4.2 Hz ), 128.3 (d, J = 8.3 Hz),
C-F C-F C-F
124.8 (d, J = 1 Hz), 124.3 (d, J = 3.4 Hz), 116.0 (d, J = 22.7 Hz), 61.6, 61.5, 56.95 (d,
C-F C-F C-F
J =1.9 Hz), 45.1 (d, J = 0.6 Hz), 34.4, 30.4, 13.90, 13.87; 19F NMR (376 MHz, CDCl ) δ
C-F C-F 3
–116.05; FT-IR (thin film, neat): 3387, 2960, 1760, 1732, 1595, 1436, 1371, 1236, 1121,
871, 757 cm-1; HRMS (ESI): m/z calcd for C H F O [M+H]+ : 491.2609; found : 491.2625.
28 37 2 5
diethyl 2-((4-cyanophenyl)(3,5-di-tert-butyl-4-hydroxyphenyl)methyl)malonate (3m)
The reaction was performed at 0.094 mmol scale of 1m; R = 0.2 (5%
f
EtOAc in hexane); yellow solid (39 mg, 88% yield); m. p. = 200–203 ºC;
1H NMR (400 MHz, CDCl3) δ 7.57 (d, J = 8.2 Hz, 2H), 7.42 (d, J = 8.2
Hz, 2H), 7.01 (s, 2H), 5.12 (s, 1H), 4.70 (d, J = 12.1 Hz, 1H), 4.25 (d, J = 12.1 Hz, 1H), 4.05
– 3.94 (m, 4H), 1.38 (s, 18H), 1.05 (t, J = 7.1 Hz, 3H), 0.96 (t, J = 7.1 Hz, 3H); 13C NMR
S8
(100 MHz, CDCl ) δ 167.6, 167.5, 153.1, 147.7, 136.2, 132.5, 130.2, 128.7, 124.5, 118.9,
3
110.6, 61.8, 61.7, 57.6, 51.3, 34.5, 30.3, 14.0, 13.9; FT-IR (thin film, neat): 3406, 2959,
2925, 2229, 1755, 1732, 1607, 1436, 1368, 1312, 1259, 1177, 1156, 1122, 1035 cm–1; HRMS
(ESI): m/z calcd for C H NO [M-H]+ : 478.2593; found : 478.2581.
29 36 5
Diethyl 2-((3,5-di-tert-butyl-4-hydroxyphenyl)(naphthalen-2-yl)methyl)malonate (3n)
The reaction was performed at 0.0581mmol scale of 1n; R = 0.2 (5%
f
EtOAc in hexane); pale yellow gummy solid (23.2 mg, 79% yield); 1H
NMR (400 MHz, CDCl ) δ 8.38 (d, J = 8.8 Hz, 1H), 7.80 (d, J = 8.0 Hz,
3
1H), 7.71 (d, J = 8.1 Hz, 1H), 7.55 – 7.50 (m, 2H), 7.46 – 7.42 (m, 2H), 7.17 (s, 2H), 5.54 (d,
J = 12.1 Hz, 1H), 5.02 (s, 1H), 4.45 (d, J = 12.1 Hz, 1H), 4.02 – 3.94 (m, 2H), 3.93 – 3.84 (m,
2H), 1.36 (s, 18H), 0.97 (t, J = 7.1 Hz, 3H), 0.83 (t, J = 7.1 Hz, 3H); 13C NMR (100 MHz,
CDCl ) δ 168.5, 167.8, 152.7, 138.1, 135.6, 134.3, 131.9, 131.0, 128.8, 127.5, 126.2, 125.6,
3
125.2, 124.9, 124.0, 123.1, 61.5, 58.9, 46.0, 34.4, 30.4, 29.8, 13.9, 13.8; FT-IR (thin film,
neat): 3441, 2959, 1758, 1732, 1599, 1435, 1368, 1254, 1155, 1036, 872, 777, 733 cm-1;
HRMS (ESI): m/z calcd for C32H40NaO5 [M+Na]+ : 527.2773; found : 527.2751.
Diethyl 2-((3,5-di-tert-butyl-4-hydroxyphenyl)(4,6-dihydropyren-1-yl)methyl)malonate
(3o)
The reaction was performed at 0.0478 mmol scale of 1o; R = 0.2 (10% EtOAc
f
in hexane); orange gummy solid (25.2 mg, 91% yield); 1H NMR (400 MHz,
CDCl ) δ 8.70 (d, J= 9.5 Hz, 1H), 8.17 – 8.14 (m, 3H), 8.07 (d, J = 8.1 Hz,
3
1H), 8.01 – 7.96 (m, 3H), 7.26 (s, 2H), 7.24 (s, 1H), 5.88 (d, J = 12.0 Hz, 1H), 5.00 (s, 1H),
4.66 (d, J = 12.1 Hz, 1H), 4.06 (q, J = 7.1 Hz, 2H), 3.77 (q, J = 7.1 Hz, 2H), 1.35 (s, 18H),
1.04 (t, J = 7.1 Hz, 3H), 0.72 (t, J = 7.0 Hz, 3H); 13C NMR (100 MHz, CDCl ) δ 168.4,
3
167.8, 152.6, 136.0, 135.8, 131.7, 131.5, 130.9, 130.1, 128.9, 127.7, 127.5, 127.2, 126.0,
125.4, 125.2, 125.04, 124.96 , 124.7 (2C), 123.9, 123.4, 61.6, 61.5, 58.9, 46.1, 34.4, 30.4,
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14.0, 13.7; FT-IR (thin film, neat): 3388, 2961, 2924, 1760, 1731, 1598, 1436, 1120, 848,
799, 723 cm-1; HRMS (ESI): m/z calcd for C H NaO [M+Na]+ : 601.2930; found :
38 42 5
601.2903.
5. Characterisation of products (13a to 13d)
3-((3,5-di-tert-butyl-4-hydroxyphenyl)(4-methoxyphenyl)methyl)pentane-2,4-dione (13a)
The reaction was performed at 0.062 mmol scale of 1a; R = 0.4 (10%
f
EtOAc in hexane); brown solid (24.6 mg, 95% yield); m. p. = 114–117
ºC; 1H NMR (400 MHz, CDCl ) δ 7.18 (d, J = 8.5 Hz, 2H), 7.00 (s, 2H),
3
6.80 (d, J = 8.5 Hz, 2H), 5.07 (s, 1H), 4.64 (s, 2H), 3.75 (s, 3H), 1.99 (s, 3H), 1.94 (s, 3H),
1.38 (s, 18H); 13C NMR (100 MHz, CDCl ) δ 203.8, 203.7, 158.4, 152.6, 136.2, 134.2, 132.1,
3
128.8, 124.2, 114.3, 75.4, 55.3, 51.0, 34.5, 30.4, 30.1, 29.9; FT-IR (thin film, neat): 3636,
2958, 1698, 1611, 1513, 1436, 1357, 1252, 1180, 1154, 1120, 1035, 889, 835, 770, 738, 642,
539 cm-1; HRMS (ESI): m/z calcd for C H O [M-H]+ : 423.2535; found : 423.2517.
27 35 4
2-((3,5-di-tert-butyl-4-hydroxyphenyl)(4-methoxyphenyl)methyl)malononitrile (13b)
The reaction was performed at 0.062 mmol scale of 1a; R = 0.4 (10%
f
EtOAc in hexane); yellow solid (23.6mg, 98% yield); m. p. = 132–134ºC;
1H NMR (400 MHz, CDCl ) δ 7.29 (d, J = 8.6 Hz, 2H), 7.11 (s, 2H), 6.92
3
(d, J = 8.6 Hz, 2H), 5.27 (s, 1H), 4.50 (d, J = 7.5 Hz, 1H), 4.30 (d, J = 7.5 Hz, 1H), 3.81 (s,
3H), 1.42 (s, 18H); 13C NMR (100 MHz, CDCl ) δ 159.6, 153.9, 136.5, 129.8, 129.2, 128.1,
3
124.7, 114.6, 112.5, 55.4, 51.2, 34.6, 30.3, 30.1; FT-IR (thin film, neat): 3626, 2961, 2255,
2203, 1710, 1612, 1515, 1437, 1363, 1307, 1254, 1182, 1157, 1121, 1034, 836, 773, 738, 635
cm-1; HRMS (ESI): m/z calcd for C H N O [M-H]+ : 389.2229; found : 389.2212.
25 29 2 2

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