Palladium-catalyzed C-H activation of N-Allyl Imines: Regioselective allylic alkylations to deliver substituted aza-1,3-dienes

Article abstract of DOI:10.1002/anie.201501322

A new mode of activation of an imine via a rare aza-substituted π-allyl complex is described. Palladium-catalyzed C(sp³)-H activation of the N-allyl imine and the subsequent nucleophilic attack by the α-alkyl cyanoester produced the 1-aza-1,3-d

Full text of DOI:10.1002/anie.201501322

Supporting Information
German Edition:
DOI:
À
Palladium-Catalyzed C H Activation of N-Allyl Imines:
Regioselective Allylic Alkylations to Deliver Substituted
Aza-1,3-Dienes**
Barry M. Trost,* Subham Mahapatra, and Martin Hansen
anie_201501322_sm_miscellaneous_information.pdf

Contents:
Experimentals:
page
General ..…………………………………………………………………………….3
General Method for Synthesis of Cyanoester Nucleophiles: ..…………………………3
General Method for Synthesis of Imines: ..……………………………………………….5
General Method for Synthesis of !-Amino Ester via Oxidative C-H Activation: ..……11
Test of Diastereoselectivity for Imine addition by Lewis Acid Activation: ..…………...21
General Method for Synthesis of 2-Aza Diene via Oxidative C-H Activation: ..………21
General Method for Synthesis of Pyridine Derivatives: ………………………………...24
References: ………………………………………………………………………………….26
1
13
H and C NMR Spectra:
Compound Page #
#
Compound
Page #
Compound Page #
#
#
S17
S18
S19
S20
S21
S22
S23
3
4
5
6
7
2
27
29
31
33
35
37
39
41
43
45
47
49
51
53
55
57
59
61
63
65
67
69
71
73
75
77
79
81
83
85
87
89
91
93
95
97
99
101
15
16
17
18
19
20
21
22
23
24
26
27
28
29
30
31
33
34
103
105
107
109
111
113
115
117
119
121
123
125
127
129
131
133
135
137
S1
S2
S3
2
5
S4
1
S5
S6
S7
S8
S9
S10
S11
S12
S13
S14
S15
S16
8
9
10
11
12
13
14
S2

General: All reactions were performed in flame- or oven-dried glassware with magnetic
stirring under nitrogen or argon atmosphere using freshly distilled solvents. THF was
distilled over sodium and CH Cl was obtained from a solvent purification system. All
2 2
commercial reagents were used without purification unless otherwise noted. Air and
moisture sensitive liquids and solutions were transferred via stainless steel syringe or
cannula and introduced into the reaction vessel through rubber septa. Thin-layer
chromatography was performed on EMD silica gel 60 F254 plates (0.25 mm); visualization
of the developed chromatogram was performed by fluorescence quenching and staining
with aqueous ceric ammonium molybdate, p-anisaldehyde, or potassium permanganate.
Organic solutions were concentrated by rotary evaporation below 40 ºC at ca. 25 mm
Hg. Chromatographic purification of products was accomplished using forced-flow
chromatography on Silicycle silica gel (particle size 0.040-0.063 µm). All isolated and
1
characterized compounds were >95% pure as judged by H NMR spectroscopic
analysis. Melting points were determined on a Thomas Hoover Capillary Melting Point
1
13
Apparatus and are uncorrected. H and C NMR spectroscopy were performed on a
Varian Mercury NMR operating at 400 and 100 MHz, respectively. Chemical shifts are
reported in ppm relative to the residual protiated solvent (CDCl3: δ
7
H
= 7.26 ppm, δ
7.16 ppm); all C NMR spectra are proton decoupled. Data for H are reported in terms
of chemical shift (δ ppm), multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, sept
C
=
1
3
1
1
3
=
septet, m = multiplet), coupling constant, and integration; data for C are reported in
terms of chemical shift. Infrared spectroscopic data was recorded as thin films on
sodium chloride plates on a Thermo Scientific Nicolet IR100 FT-IR spectrometer. High-
resolution mass spectrometry (HRMS) was measured on a Bruker micrOTOF-Q II
electronspray ionization (ESI) mass spectrometer by the Vincent Coates Foundation
Mass Spectrometry Laboratory at Stanford University. Mass peaks are reported in m/z
units.
General Method for Synthesis of Cyanoester Nucleophiles:
O
NC
1) LDA, THF
) di-t-butyl
dicarbonate
NC
O
2
R
R
To a stirred solution of nitrile (10.0 mmol, 1.0 equiv.) in THF (30.0 mL) at -78 ºC was
cannulated a solution of LDA (25.0 mL, 25.0 mmol, 1M in THF, 2.5 equiv.). After 30 min,
the reaction was warmed to rt. After another 30 min, the reaction was cooled back down
to -78 ºC. A solution of di-t-butyl dicarbonate (2.30 g, 10.5 mmol, 1.05 equiv.) in THF (20
mL) was added dropwise. After 3 h, the reaction mixture was quenched with satd. aq.
NH
organic extract was washed with 10% aq. HCl (2 X 30 mL) and brine (30 mL). The dried
extract (MgSO ) was concentrated in vacuo and was purified by flash chromatography
4 2
Cl (25 mL) and aqueous layer was extracted with Et O (2 X 40 mL). The combined
4
over silica gel, eluting with 5-10% EtOAC / hexanes to give desired cyanoesters (2, S1-
S3, 25) as colorless oils.
S3

O
NC
O
Me
2
t-Butyl 2-cyanopropanoate (2): Obtained as colorless oil (1.35 g, 8.70 mmol, 87%).
1
1
Previously reported compound: H NMR (400 MHz; CDCl3): δ 3.44 (q, J = 7.4 Hz, 1H),
1
3
1
8
3
.53 (d, J = 7.4 Hz, 3H), 1.49 (s, 9H) ppm; C NMR (100 MHz, CDCl ) δ 165.6, 117.9,
4.0, 32.6, 27.9, 15.4 ppm.
O
NC
O
n-Hex
S1
t-Butyl 2-cyanooctanoate (S1): Obtained as colorless oil (2.06 g, 9.14 mmol, 91%).
1
1
Previously reported compound: H NMR (400 MHz; CDCl3): δ 3.38 (t, J = 7.0 Hz, 1H),
.89 (q, J = 7.6 Hz, 2H), 1.44-1.49 (m, 11H), 1.29-1.37 (m, 6H), 0.88 (t, J = 6.8 Hz, 3H)
1
1
3
ppm; C NMR (100 MHz, CDCl
2.6, 14.1 ppm.
3
) δ 165.4, 117.1, 84.0, 38.7, 31.5, 30.0, 28.6, 27.9, 26.8,
2
O
NC
O
S2
t-Butyl-2-cyano-3-methylbutanoate (S2): Obtained as colorless oil (1.70 g, 9.28 mmol,
2
1
9
3%). Previously reported compound: H NMR (400 MHz; CDCl3): δ 3.29 (d, J = 5.4
Hz, 1H), 2.33-2.41 (m, 1H), 1.50 (s, 9H), 1.12 (d, J = 6.8 Hz, 3H), 1.09 (d, J = 6.7 Hz,
1
3
3
H) ppm; C NMR (100 MHz, CDCl
3
) δ 165.0, 115.9, 83.9, 46.5, 30.1, 27.9, 20.8, 18.9
ppm.
O
NC
O
S3
t-Butyl 2-cyano-3-phenylpropanoate (S3): Obtained as colorless oil (2.27 g, 9.81
1
1
mmol, 98%). Previously reported compound: H NMR (400 MHz; CDCl3): δ 7.27-7.36
(
1
1
m, 5H), 3.63 (dd, J = 8.3, 6.0 Hz, 1H), 3.24 (dd, J = 13.9, 6.0 Hz, 1H), 3.16 (dd, J =
1
3
3.9, 8.3 Hz, 1H), 1.44 (s, 9H) ppm; C NMR (100 MHz, CDCl
28.9, 127.8, 116.7, 84.4, 40.6, 35.9, 27.9 ppm.
3
) δ 164.5, 135.6, 129.2,
S4

O
NC
O
2
5
t-Butyl 2-cyano-2-phenylacetate (25): Obtained as colorless oil (2.07 g, 9.53 mmol,
1
1
9
4
1
5%). Previously reported compound: H NMR (400 MHz; CDCl3): δ 7.38-7.46 (m, 5H),
1
3
.61 (s, 1H), 1.44 (s, 9H) ppm; C NMR (100 MHz, CDCl
27.8, 116.1, 84.6, 44.9, 27.7 ppm.
3
) δ 164.0, 130.5, 129.3, 129.1,
O
allyl bromide
NaO Bu, THF
O
t
NC
O
NC
O
S4
t
t-Butyl-2-cyanopent-4-enoate (S4): To a stirred suspension of NaO Bu (961 mg, 10.0
mmol, 1.0 equiv.) in THF (40 mL) at 0 ºC was added t-butyl 2-cyanoacetate (1.41 g, 10.0
mmol, 1 equiv.) slowly. After 30 min, allyl bromide (1.21 g, 10.0 mmol, 1.0 equiv.) was
added dropwise. After 3 h, the reaction was quenched with H
2
O (25 mL) and aqueous
) was concentrated
layer was extracted with Et O (2 X 30 mL). The dried extract (MgSO
2
4
in vacuo and was purified by flash chromatography over silica gel, eluting with 2-5%
EtOAC / hexanes to give cyanoester S4 (783 mg, 4.32 mmol, 43%) as colorless oil.
2
1
Previously reported compound: H NMR (400 MHz; CDCl3): δ 5.81 (ddt, J = 17.1, 10.1,
7
9
2
.0 Hz, 1H), 5.21-5.28 (m, 2H), 3.46 (dd, J = 7.2, 6.3 Hz, 1H), 2.62-2.67 (m, 2H), 1.49 (s,
1
3
H) ppm; C NMR (100 MHz, CDCl
7.9 ppm.
3
) δ 164.6, 131.7, 119.9, 116.6, 84.3, 38.5, 34.1,
General Method for Synthesis of Imines:
allyl amine
MgSO , CH Cl
2
4
2
R
O
R
N
To a stirred solution of aldehyde (10.0 mmol, 1.0 equiv.) in CH
MgSO4 (1.0 g) followed by allyl amine (0.82 mL, 628 mg, 11.0 mmol, 1.1 equiv.). After
4 h, the reaction was filtered through a sintered glass funnel. Solvent was removed in
2 2
Cl (12 mL) was added
2
vacuo and kept under high vacuum for 3 h. The crude was sufficiently clean (>95% purity
by NMR) and was directly used for oxidative C-H activation.
N
1
(
E)-N-Allyl-1-phenylmethanimine (1): Obtained as colorless oil (1.45 g, quant.).
3
1
Previously reported compound: H NMR (400 MHz; CDCl3): δ 8.30 (t, J = 1.3 Hz, 1H),
7
1
.75-7.78 (m, 2H), 7.40-7.44 (m, 3H), 6.08 (ddt, J = 17.2, 10.3, 5.7 Hz, 1H), 5.25 (dq, J =
1
3
7.2, 1.7 Hz, 1H), 5.17 (dq, J = 10.3, 1.6 Hz, 1H), 4.27 (dq, J = 5.7, 1.5 Hz, 2H) ppm;
C
NMR (100 MHz, CDCl
3
) δ 162.1, 136.2, 135.9, 130.8, 128.6, 128.2, 116.1, 63.6 ppm.
S5

N
F
S5
(
E)-N-Allyl-1-(4-fluorophenyl)methanimine (S5): Obtained as colorless oil (1.63 g,
4
1
quant.). Previously reported compound: H NMR (400 MHz; CDCl3): δ 8.25 (t, J = 1.2
Hz, 1H), 7.72-7.76 (m, 2H), 7.06-7.12 (m, 2H), 6.06 (ddt, J = 17.2, 10.3, 5.7 Hz, 1H),
5
2
.23 (dq, J = 17.2, 1.7 Hz, 1H), 5.16 (dq, J = 10.3, 1.6 Hz, 1H), 4.24 (dq, J = 5.7, 1.5 Hz,
H) ppm; C NMR (100 MHz, CDCl ) δ 164.4 (d, J = 249.5 Hz), 160.6, 135.9, 132.5 (d,
3
1
3
J = 2.9 Hz), 130.1 (d, J = 9.0 Hz), 116.1 (d, J = 35.9 Hz), 115.7, 63.5 ppm.
N
Cl
S6
(
E)-N-Allyl-1-(4-chlorophenyl)methanimine (S6): Obtained as colorless oil (1.79 g,
5
1
quant.). Previously reported compound: H NMR (400 MHz; CDCl3): δ 8.23 (t, J = 1.3
Hz, 1H), 7.66-7.69 (m, 2H), 7.35-7.39 (m, 2H), 6.05 (ddt, J = 17.2, 10.3, 5.7 Hz, 1H),
5
2
6
.23 (dq, J = 17.2, 1.7 Hz, 1H), 5.16 (dq, J = 10.3, 1.6 Hz, 1H), 4.24 (dq, J = 5.7, 1.5 Hz,
1
3
H) ppm; C NMR (100 MHz, CDCl
3.5 ppm.
3
) δ 160.6, 136.7, 135.7, 134.7, 129.4, 128.9, 116.3,
N
Br
S7
(
E)-N-Allyl-1-(4-bromophenyl)methanimine (S7): ): Obtained as light yellow oil (2.25
5
1
g, quant.). Previously reported compound: H NMR (400 MHz; CDCl3): δ 8.23 (s, 1H),
7
1
.60-7.63 (m, 2H), 7.52-7.55 (m, 2H), 6.05 (ddt, J = 17.2, 10.3, 5.7 Hz, 1H), 5.23 (dq, J =
1
3
7.2, 1.7 Hz, 1H), 5.16 (dq, J = 10.3, 1.6 Hz, 1H), 4.24 (dq, J = 5.7, 1.5 Hz, 2H) ppm;
C
NMR (100 MHz, CDCl
3
) δ 160.8, 135.7, 135.1, 131.9, 129.6, 125.2, 116.4, 63.6 ppm.
N
O N
2
S8
(
E)-N-Allyl-1-(4-nitrophenyl)methanimine (S8): Obtained as pale yellow solid (1.89 g,
6
1
quant.). Previously reported compound: H NMR (400 MHz; CDCl3): δ 8.37 (t, J = 1.4
Hz, 1H), 8.23-8.26 (m, 2H), 7.89-7.92 (m, 2H), 6.06 (ddt, J = 17.2, 10.3, 5.7 Hz, 1H),
5
2
6
.24 (dq, J = 17.2, 1.7 Hz, 1H), 5.18 (dq, J = 10.3, 1.5 Hz, 1H), 4.31 (dq, J = 5.7, 1.5 Hz,
1
3
H) ppm; C NMR (100 MHz, CDCl
3.7 ppm.
3
) δ 159.6, 149.1, 141.7, 135.2, 128.9, 123.9, 116.8,
N
NO2
S9
(
E)-N-Allyl-1-(3-nitrophenyl)methanimine (S9): Obtained as pale yellow oil (1.90 g,
-
1
1
quant.). IR: (neat) 3041, 2970, 2940, 2835, 1626, 1508, 1420, 1332, 980, 907 cm ; H
S6

NMR (400 MHz; CDCl3): δ 8.56 (t, J = 1.9 Hz, 1H), 8.36 (s, 1H), 8.24 (ddd, J = 8.2, 2.3,
1
1
.1 Hz, 1H), 8.08 (dt, J = 7.7, 1.2 Hz, 1H), 7.58 (t, J = 7.9 Hz, 1H), 6.06 (d dt, J = 17.2,
0.3, 5.7 Hz, 1H), 5.24 (dq, J = 17.2, 1.7 Hz, 1H), 5.17 (dq, J = 10.3, 1.5 Hz, 1H), 4.30
1
3
(
dq, J = 5.7, 1.5 Hz, 2H) ppm; C NMR (100 MHz, CDCl
3
) δ 159.3, 148.6, 137.9, 135.3,
33.6, 129.7, 125.1, 122.9, 116.7, 63.5 ppm; HRMS (ESI+) calcd. for C10 (M+H)
91.0815, found 191.0810.
1
1
11 2 2
H N O
N
NO2
S10
(
E)-N-Allyl-1-(2-nitrophenyl)methanimine (S10): Obtained as pale yellow oil (1.89 g,
7
1
quant.). Previously reported compound: H NMR (400 MHz; CDCl3): δ 8.69 (s, 1H),
.06 (dd, J = 7.8, 1.5 Hz, 1H), 7.97 (dd, J = 8.2, 1.3 Hz, 1H), 7.61-7.66 (m, 1H), 7.53
ddd, J = 8.1, 7.4, 1.5 Hz, 1H), 6.05 (ddt, J = 17.2, 10.3, 5.7 Hz, 1H), 5.23 (dq, J = 17.2,
8
(
1
1
3
.7 Hz, 1H), 5.16 (dq, J = 10.3, 1.5 Hz, 1H), 4.30 (dq, J = 5.7, 1.5 Hz, 2H) ppm; C NMR
(
100 MHz, CDCl
3
) 157.7, 148.9, 135.2, 133.5, 131.1, 130.7, 129.7, 124.3, 116.7, 63.5
ppm.
N
F C
3
S11
(
(
E)-N-Allyl-1-(4-(trifluoromethyl)phenyl)methanimine (S11): Obtained as colorless oil
2.13 g, quant.). Previously reported compound: H NMR (400 MHz; CDCl3): δ 8.33 (s,
8
1
1
1
1
H), 7.86 (d, J = 8.0 Hz, 2H), 7.66 (d, J = 8.1 Hz, 2H), 6.07 (ddt, J = 17.2, 10.3, 5.7 Hz,
H), 5.24 (dq, J = 17.2, 1.7 Hz, 1H), 5.18 (dq, J = 10.3, 1.5 Hz, 1H), 4.29 (dq, J = 5.7,
.5 Hz, 2H) ppm; C NMR (100 MHz, CDCl ) δ 160.5, 139.4, 135.5, 132.3 (q, J = 32.3
3
1
3
Hz), 128.4, 125.7 (q, J = 4.0 Hz), 124.0 (q, J = 270.5 Hz), 116.5, 63.7 ppm.
N
Me
S12
(
E)-N-Allyl-1-(p-tolyl)methanimine (S12): Obtained as colorless oil (1.59 g, quant.).
4
1
Previously reported compound: H NMR (400 MHz; CDCl3): δ 8.26 (s, 1H), 7.64-7.67
m, 2H), 7.22 (d, J = 7.8 Hz, 2H), 6.08 (ddt, J = 17.2, 10.3, 5.7 Hz, 1H), 5.24 (dq, J =
(
1
3
6
7.2, 1.7 Hz, 1H), 5.16 (dq, J = 10.3, 1.6 Hz, 1H), 4.25 (dq, J = 5.7, 1.5 Hz, 2H), 2.38 (s,
1
3
H) ppm; C NMR (100 MHz, CDCl
3.6, 21.6 ppm.
3
) δ 162.0, 141.0, 136.1, 133.6, 129.4, 128.2, 116.0,
N
MeO
S13
(
E)-N-Allyl-1-(4-methoxyphenyl)methanimine (S13): Obtained as colorless oil (1.75 g,
8
1
quant.). Previously reported compound: H NMR (400 MHz; CDCl3): δ 8.22 (s, 1H),
7
1
.68-7.71 (m, 2H), 6.90-6.94 (m, 2H), 6.06 (ddt, J = 17.2, 10.3, 5.7 Hz, 1H), 5.23 (dq, J =
7.2, 1.7 Hz, 1H), 5.14 (dq, J = 10.2, 1.6 Hz, 1H), 4.22 (dq, J = 5.7, 1.5 Hz, 2H), 3.83 (s,
S7

1
3
3
6
H) ppm; C NMR (100 MHz, CDCl
3.6, 55.4 ppm.
3
) δ 161.7, 161.4, 136.3, 129.8, 129.2, 116.0, 114.1,
N
S14
(
E)-N-Allyl-1-(naphthalen-1-yl)methanimine (S14): Obtained as light yellow oil (1.96 g,
9
1
quant.). Previously reported compound: H NMR (400 MHz; CDCl3): δ 8.97 (d, J = 8.5
Hz, 1H), 8.96 (s, 1H), 7.90-7.96 (m, 3H), 7.62 (ddd, J = 8.5, 6.9, 1.5 Hz, 1H), 7.52-7.57
(
m, 2H), 6.22 (ddt, J = 17.2, 10.3, 5.6 Hz, 1H), 5.37 (dq, J = 17.2, 1.8 Hz, 1H), 5.25 (dq,
1
3
J = 10.3, 1.6 Hz, 1H), 4.42 (dq, J = 5.6, 1.6 Hz, 2H) ppm; C NMR (100 MHz, CDCl
1
1
3
) δ
61.6, 136.2, 133.8, 131.6, 131.3, 131.1, 128.8, 128.6, 127.2, 126.1, 125.3, 124.3,
16.0, 64.5 ppm.
N
S15
(
E)-N-Allyl-1-(naphthalen-2-yl)methanimine (S15): Obtained as white solid (1.95 g,
9
1
quant.). Previously reported compound: H NMR (400 MHz; CDCl3): δ 8.45 (s, 1H),
.06 (s, 1H), 8.03 (dd, J = 8.5, 1.6 Hz, 1H), 7.85-7.91 (m, 3H), 7.49-7.55 (m, 2H), 6.13
ddt, J = 17.2, 10.3, 5.7 Hz, 1H), 5.29 (dq, J = 17.2, 1.7 Hz, 1H), 5.20 (dq, J = 10.3, 1.6
8
(
1
3
Hz, 1H), 4.33 (dq, J = 5.7, 1.5 Hz, 2H) ppm; C NMR (100 MHz, CDCl
3
) δ 162.2, 136.0,
1
34.8, 133.9, 133.2, 130.1, 128.7, 128.6, 128.0, 127.2, 126.6, 123.9, 116.3, 63.7 ppm.
N
O
S16
(
E)-N-Allyl-1-(furan-2-yl)methanimine (S16): Obtained as light yellow oil (1.34 g,
1
0 1
quant.) Previously reported compound:
H NMR (400 MHz; CDCl3): δ 8.08 (s, 1H),
7
6
=
1
.49 (d, J = 1.6 Hz, 1H), 6.74 (d, J = 3.4 Hz, 1H), 6.46 (dd, J = 3.4, 1.8 Hz, 1H), 5.99-
.09 (m, 1H), 5.20 (dq, J = 17.2, 1.7 Hz, 1H), 5.13 (dq, J = 10.2, 1.5 Hz, 1H), 4.21 (dq, J
1
3
5.9, 1.4 Hz, 2H) ppm; C NMR (100 MHz, CDCl
14.0, 111.7, 63.7 ppm.
3
) δ 151.7, 150.4, 144.8, 135.6, 116.5,
N
N
S17
(
E)-N-Allyl-1-(pyridin-4-yl)methanimine (S17): Obtained as colorless oil (1.47 g,
1
1 1
quant.). Previously reported compound:
H NMR (400 MHz; CDCl3): δ 8.69 (dd, J =
6
5
5
1
.0, 2.8 Hz, 2H), 8.26 (s, 1H), 7.60 (dd, J = 6.0, 2.8 Hz, 2H), 6.06 (ddt, J = 17.2, 10.3,
.7 Hz, 1H), 5.24 (dq, J = 17.2, 1.7 Hz, 1H), 5.18 (dq, J = 10.3, 1.5 Hz, 1H), 4.29 (dq, J =
1
3
.7, 1.5 Hz, 2H) ppm; C NMR (100 MHz, CDCl
16.5, 63.4 ppm.
3
) δ 159.7, 150.3, 142.7, 134.9, 121.7,
S8

N
N
PhO2S
S18
(
E)-N-Allyl-1-(1-(phenylsulfonyl)-1H-indol-3-yl)methanimine (S18): Obtained as pale
yellow solid (3.24 g, quant.). IR: (neat) 3075, 2788, 1621, 1456, 1428, 1354, 1229, 1163,
-
1 1
1
7
7
1
108, 1081 cm ; H NMR (400 MHz; CDCl3): δ 8.45 (t, J = 1.3 Hz, 1H), 8.37 (ddd, J =
.8, 1.4, 0.7 Hz, 1H), 7.99 (dt, J = 8.2, 0.9 Hz, 1H), 7.90-7.93 (m, 2H), 7.85 (s, 1H), 7.52-
.57 (m, 1H), 7.42-7.47 (m, 2H), 7.38 (ddd, J = 8.3, 7.2, 1.2 Hz, 1H), 7.31 (td, J = 7.5,
.1 Hz, 1H), 6.09 (ddt, J = 17.2, 10.3, 5.5 Hz, 1H), 5.26 (dq, J = 17.2, 1.8 Hz, 1H), 5.16
1
3
(
dq, J = 10.3, 1.7 Hz, 1H), 4.26 (dq, J = 5.5, 1.5 Hz, 2H) ppm; C NMR (100 MHz,
CDCl ) δ 155.0, 138.0, 136.2, 135.6, 134.3, 129.6, 129.5, 128.1, 127.0, 125.8, 124.4,
23.2, 120.9, 115.9, 113.3, 64.3 ppm; HRMS (ESI+) calcd. for C18 S (M+H)
25.1005, found 325.1010.
3
1
3
17 2 2
H N O
N
S19
(
E)-N-Allyl-1-(cyclohex-1-en-1-yl)methanimine (S19): Obtained as colorless oil (1.49
-
1
g, quant.). IR: (neat) 2889, 2818, 2792, 1625, 1605, 1413, 1281, 1174, 1006, 978 cm ;
1
H NMR (400 MHz; CDCl3): δ 7.77 (s, 1H), 6.13 (tt, J = 3.8, 1.8 Hz, 1H), 5.97
(ddt, J = 17.2, 10.3, 5.7 Hz, 1H), 5.13 (dq, J = 17.2, 1.8 Hz, 1H), 5.06 (dq, J =
1
2
1
0.2, 1.6 Hz, 1H), 4.06 (dd, J = 5.6, 0.9 Hz, 2H), 2.27-2.30 (m, 2H), 2.18-2.21 (m,
1
3
H), 1.59-1.67 (m, 4H) ppm; C NMR (100 MHz, CDCl
3
) δ 165.5, 139.0, 138.1,
36.4, 115.6, 63.4, 26.1, 23.8, 22.5, 22.1 ppm; HRMS (ESI+) calcd. for C10
16
H N
(
M+H) 150.1277, found 150.1273.
N
S20
(
E)-N-Allyl-1-(cyclopent-1-en-1-yl)methanimine (S20): Obtained as colorless oil (1.35
1
2 1
g, quant.). Previously reported compound. H NMR (400 MHz, CDCl
3
) δ 8.07 (s, 1H),
.17 (quintet, J = 2.2 Hz, 1H), 5.97 (ddt, J = 17.2, 10.3, 5.8 Hz, 1H), 5.12 (dq, J = 17.2,
.7 Hz, 1H), 5.07 (dq, J = 10.2, 1.6 Hz, 1H), 4.08 (d, J = 5.6 Hz, 2H), 2.55-2.60 (m, 2H),
6
1
2
1
1
3
3
.44-2.49 (m, 2H), 1.92 (quintet, J = 7.6 Hz, 2H) ppm; C NMR (100 MHz, CDCl ) δ
59.9, 144.5, 140.7, 136.1, 115.8, 63.7, 33.3, 30.6, 23.1 ppm.
N
S21
(
E)-N-Allyl-1-cyclohexylmethanimine (S21): Obtained as colorless oil (1.52 g, quant.).
1
3 1
Previously reported compound. H NMR (400 MHz; CDCl3): δ 7.50 (dt, J = 4.9, 1.2 Hz,
1
1
1
2
H), 5.94 (ddt, J = 17.2, 10.3, 5.7 Hz, 1H), 5.11 (dq, J = 17.2, 1.8 Hz, 1H), 5.06 (dq, J =
0.3, 1.6 Hz, 1H), 3.96 (dq, J = 5.7, 1.5 Hz, 2H), 2.12-2.21 (m, 1H), 1.62-1.82 (m, 5H),
1
3
.15-1.33 (m, 5H) ppm; C NMR (100 MHz, CDCl
9.8, 26.1, 25.6 ppm.
3
) δ 170.2, 136.3, 115.6, 63.5, 43.6,
S9

Br
Br
1)
Me
n-BuLi, THF
TMS
O
2) DMF,
n-BuLi, THF
TMS
S22
2
-(4-(Trimethylsilyl)but-3-yn-1-yl)benzaldehyde (S22): To a stirred solution of 1-(tri-
methylsilyl)propyne (1.25 g, 11.1 mmol, 1.05 equiv.) in THF (35.0 mL) at -78 ºC was
added n-BuLi (4.4 mL, 11.1 mmol, 2.51 M in hexanes, 1.05 equiv.) dropwise. After 2 h, a
solution of 2-bromobenzylbromide (2.65 g, 10.6 mmol, 1.0 equiv.) in THF (4.0 mL) was
cannulated over 15 min. The reaction was allowed to warm to rt. After 15 h, the solvent
was removed in vacuo and the residue was purified by flash chromatography over silica
1
4
gel, eluting with 2-5% EtOAc / hexanes to give known intermediate aryl bromide (2.65
g, 9.42 mmol, 89%) as colorless oil.
To a stirred solution of intermediate aryl bromide (2.60 g, 9.24 mmol, 1.0 equiv.)
in THF (10 mL) at -78 ºC was added n-BuLi (5.5 mL, 13.8 mmol, 2.51 M in hexanes, 1.5
equiv.) dropwise. After 30 min, DMF (1.69 g, 23.1 mmol, 2.5 equiv.) was added dropwise
and the reaction was warmed to rt. After 16 h, the reaction was poured into a mixture of
satd. aq. NH4Cl and Et2O (50 mL, 1:1) and the aqueous layer was extracted with Et
2
O
(
2 X 30 mL). The dried extract (MgSO ) was concentrated in vacuo and was purified by
4
flash chromatography over silica gel, eluting with 5-10% EtOAC / hexanes to give
aldehyde S22 (1.72 g, 7.47 mmol, 81 %) as colorless oil. IR: (neat) 2917, 2859, 2143,
-
1
1
1
1
673, 1578, 1552, 1232, 1175, 1025, 830 cm ; H NMR (400 MHz, CDCl
3
) δ 10.26 (s,
H), 7.84 (dd, J = 7.6, 1.5 Hz, 1H), 7.53 (td, J = 7.5, 1.5 Hz, 1H), 7.42 (td, J = 7.5, 1.2
Hz, 1H), 7.33 (dt, J = 7.6, 1.2 Hz, 1H), 3.24 (t, J = 7.1 Hz, 2H), 2.56 (t, J = 7.1 Hz, 2H),
1
3
0
1
.10 (s, 9H) ppm; C NMR (100 MHz, CDCl
3
) δ 192.6, 142.9, 134.0, 133.7, 132.6,
31.8, 127.2, 105.9, 86.4, 31.4, 22.1, 0.11 ppm; HRMS (ESI+) calcd. for C14
H
19OSi
(
M+H) 231.1200, found 231.1193.
allyl amine
MgSO , CH Cl
2
O
N
4
2
TMS
TMS
S22
S23
(
E)-N-Allyl-1-(2-(4-(trimethylsilyl)but-3-yn-1-yl)phenyl)methanimine (S23): To
a
stirred solution of aldehyde S22 (1.18 g, 5.12 mmol, 1.0 equiv.) in CH
2
Cl (6.0 mL) was
2
added MgSO4 (500 mg) followed by allyl amine (0.42 mL, 322 mg, 5.63 mmol, 1.1
equiv.). After 24 h, the reaction was filtered through a sintered glass funnel. Solvent was
removed in vacuo and kept under high vacuum for 3 h to give imine S23 (1.38 g, 5.12
mmol, quant.) as colorless oil. The crude was sufficiently clean (>95% purity by NMR)
and was directly used for oxidative C-H activation. IR: (neat) 2916, 2858, 2144, 1618,
-
1
1
1
3
425, 1232, 1026, 979, 905, 830 cm ; H NMR (400 MHz, CDCl ) δ 8.61 (s, 1H), 7.89
(
(
3
dd, J = 7.7, 1.5 Hz, 1H), 7.21-7.36 (m, 4H), 6.09 (ddt, J = 17.2, 10.3, 5.6 Hz, 1H), 5.25
dq, J = 17.2, 1.7 Hz, 1H), 5.16 (dq, J = 10.3, 1.6 Hz, 1H), 4.28 (dq, J = 5.6, 1.5 Hz, 2H),
1
3
.10 (t, J = 7.5 Hz, 2H), 2.51 (t, J = 7.5 Hz, 2H), 0.13 (s, 9H) ppm; C NMR (100 MHz,
) δ 160.4, 140.2, 136.1, 134.0, 130.6, 130.3, 128.3, 127.0, 116.0, 106.3, 85.8,
4.2, 31.8, 22.3, 0.21 ppm; HRMS (ESI+) calcd. for C17 24NSi (M+H) 270.1673, found
70.1664.
CDCl
6
2
3
H
S10

General Method for Synthesis of !-Amino Ester via Oxidative C-H Activation:
Pd(OAc)2
PPh3
NC R2
N
NC
R2
t
O Bu
N
R1
+
t
CO Bu
2
Hünig's base
R1
O
2,6-DMBQ
THF, rt
An oven dried Pyrex microwave vial was charged with Pd(OAc)
2
(0.03 equiv.),
PPh
3
(0.06 equiv.), 2,6-dimethylbenzoquinone (1.1 equiv.) and was sealed with a rubber
septa. The vial was evacuated and filled with nitrogen three times in an interval of 10
min. In a separate sealed nitrogen flushed vial, cyanoester (1.0 equiv.) and N-allyl imine
(
1.1 equiv.) were taken in freshly distilled THF. The solution was cannulated to the
microwave vial with palladium catalyst. N,N-diisopropylethylamine (1.1 equiv.) was
added to the resulting turbid solution and was allowed to stir at rt for 10-60 h depending
on the substrates. Upon completion (monitored by crude NMR), the reaction was passed
through a plug of silica gel (pre-neutralized with 2% Et
3
N in Hexanes). Solvent was
removed in vacuo and the residue was purified by flash chromatography over silica gel
(
pre-neutralized with 1% Et
3
N in Hexanes), eluting with EtOAc / hexanes, to give !-
amino-"-cyanoesters 3-24.
NC Me
N
t
O Bu
O
3
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-2-methyl-3-phenylpropanoate (3): The
reaction was performed with N-allyl imine 1 (160 mg, 1.10 mmol), cyanoester 2 (155 mg,
1
.00 mmol), Pd(OAc)
2 3
(6.7 mg, 0.030 mmol), PPh (15.7 mg, 0.060 mmol) 2,6-
dimethylbenzoquinone (150 mg, 1.10 mmol) and N,N-diisopropylethylamine (142 mg,
0
1
1
.19 mL, 1.10 mmol) in THF (5.0 mL) for 12 h. Purification by flash chromatography (5-
5% EtOAC / hexanes) gave product 3 (278 mg, 0.932 mmol, 93%) as white solid. Mp.
-
1
08-110 ºC; IR: (neat) 2940, 1710, 1622, 1435, 1351, 1261, 1240, 1140, 1108, 827 cm ;
1
H NMR (400 MHz, CDCl
3
) δ 7.87 (d, J = 8.9 Hz, 1H), 7.49-7.52 (m, 2H), 7.31-7.39 (m,
3
1
1
2
H), 6.58 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.81 (d, J = 10.2 Hz, 1H), 5.69 (dd, J = 17.4,
1
3
.0 Hz, 1H), 4.47 (s, 1H), 1.47 (s, 9H), 1.41 (s, 3H) ppm; C NMR (176 MHz, CDCl
67.9, 165.4, 137.3, 136.9, 128.9, 128.8, 128.7, 128.6, 119.0, 84.2, 78.6, 51.7, 27.9,
1.2 ppm; HRMS (ESI+) calcd. for C18 (M+H) 299.1754, found 299.1750.
3
) δ
23 2 2
H N O
NC n-Hex
t
N
O Bu
O
4
t-Butyl-2-(((E)-allylidene)amino)(phenyl)methyl)-2-cyanooctanoate (4): The reaction
was performed with N-allyl imine 1 (89.2 mg, 0.660 mmol), cyanoester S1 (135 mg,
0
.600 mmol), Pd(OAc)
2 3
(4.0 mg, 0.018 mmol), PPh (9.4 mg, 0.036 mmol) 2,6-
dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-diisopropylethylamine (85.4 mg,
1
15 µL, 0.660 mmol) in THF (3.0 mL) for 14 h. Purification by flash chromatography (5-
S11

1
5% EtOAC / hexanes) gave product 4 (168 mg, 0.456 mmol, 76%) as colorless oil. IR:
-
1 1
(
(
7
5
9
neat) 2915, 2888, 2819, 1709, 1622, 1582, 1435, 1350, 1236, 1140, 829 cm ; H NMR
400 MHz, CDCl ) δ 7.82 (dd, J = 8.9, 0.3 Hz, 1H), 7.52 (dd, J = 8.0, 1.5 Hz, 2H), 7.39-
.31 (m, 3H), 6.57 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.79 (dt, J = 10.3, 0.9 Hz, 1H), 5.69-
.65 (m, 1H), 4.44 (s, 1H), 1.83 (td, J = 12.4, 3.3 Hz, 1H), 1.49-1.55 (m, 1H), 1.47 (s,
3
1
3
H), 1.38 (td, J = 12.3, 4.1 Hz, 1H), 1.26-1.18 (m, 7H), 0.84 (t, J = 6.9 Hz, 3H) ppm;
) δ 167.7, 165.2, 137.5, 136.9, 129.0, 128.8, 128.7, 128.6, 118.4,
4.3, 79.2, 57.5, 35.2, 31.6, 29.1, 28.0, 27.9, 25.2, 22.5, 14.1 ppm; HRMS (ESI+) calcd.
C
NMR (100 MHz, CDCl
8
3
for C23
H
33
N
2
O
2
(M+H) 369.2537, found 369.2527.
NC
N
t
O Bu
O
5
t-Butyl-2-(((E)-allylidene)amino)(phenyl)methyl)-2-cyano-3-methylbutanoate
The reaction was performed with N-allyl imine 1 (95.9 mg, 0.660 mmol), cyanoester S2
110 mg, 0.600 mmol), Pd(OAc) (4.0 mg, 0.018 mmol), PPh (9.4 mg, 0.036 mmol) 2,6-
dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-diisopropylethylamine (85.4 mg,
(5):
(
2
3
1
1
15 µL, 0.660 mmol) in THF (3.0 mL) for 18 h. Purification by flash chromatography (5-
5% EtOAC / hexanes) gave product 5 (165 mg, 0.505 mmol, 84%) as colorless oil. IR:
-
1 1
(
(
neat) 2936, 2895, 1708, 1621, 1582, 1435, 1374, 1350, 1232, 1139, 829 cm ; H NMR
400 MHz, CDCl ) δ 7.84 (dd, J = 8.9, 0.5 Hz, 1H), 7.57-7.59 (m, 2H), 7.32-7.38 (m, 3H),
.56 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.78 (dt, J = 10.3, 0.9 Hz, 1H), 5.66 (dd, J = 17.4,
.1 Hz, 1H), 4.70 (s, 1H), 1.99 (quintet, J = 6.8 Hz, 1H), 1.45 (s, 9H), 1.09 (d, J = 6.7 Hz,
3
6
1
3
1
1
3
H), 0.99 (d, J = 6.8 Hz, 3H) ppm; C NMR (100 MHz, CDCl
3
) δ 165.9, 165.3, 137.9,
37.0, 128.9, 128.7, 128.5, 118.6, 84.1, 75.9, 61.3, 32.5, 28.0, 19.3, 18.3 ppm; HRMS
(
ESI+) calcd. for C20
H
27
N
2
O
2
(M+H) 327.2067, found 327.2067.
NC
N
t
O Bu
O
6
t-Butyl-2-(((E)-allylidene)amino)(phenyl)methyl)-2-cyanopent-4-enoate
reaction was performed with N-allyl imine 1 (95.9 mg, 0.660 mmol), cyanoester S4 (109
mg, 0.600 mmol), Pd(OAc) (4.0 mg, 0.018 mmol), PPh (9.4 mg, 0.036 mmol) 2,6-
dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-diisopropylethylamine (85.4 mg,
(6): The
2
3
1
1
15 µL, 0.660 mmol) in THF (3.0 mL) for 14 h. Purification by flash chromatography (5-
5% EtOAC / hexanes) gave product 6 (177 mg, 0.545 mmol, 91%) as colorless oil. IR:
-
1
1
(
neat) 2939, 1711, 1621, 1581, 1350, 1293, 1241, 1218, 1132, 829 cm ; H NMR (400
MHz, CDCl ) δ 7.84 (dd, J = 8.9, 0.4 Hz, 1H), 7.52-7.54 (m, 2H), 7.34-7.40 (m, 3H), 6.58
ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.80 (dt, J = 10.3, 0.8 Hz, 1H), 5.70-5.80 (m, 1H), 5.66-
3
(
5
=
.70 (m, 1H), 5.16-5.18 (m, 1H), 5.13 (dq, J = 4.0, 1.2 Hz, 1H), 4.48 (s, 1H), 2.56 (dd, J
13.6, 8.3 Hz, 1H), 2.18 (ddt, J = 13.6, 6.2, 1.3 Hz, 1H), 1.44 (s, 9H) ppm; C NMR
1
3
(
100 MHz, CDCl
3
) δ 166.9, 165.4, 137.3, 137.0, 130.7, 129.1, 129.03, 128.99, 128.8,
S12

1
20.7, 118.0, 84.6, 78.8, 57.1, 39.6, 28.1 ppm; HRMS (ESI+) calcd. for C20
25 2 2
H N O
(
M+H) 325.1911, found 325.1901.
Ph
O
NC
N
t
O Bu
7
t-Butyl-3-(((E)-allylidene)amino)-2-benzyl-2-cyano-3-phenylpropanoate (7): The
reaction was performed with N-allyl imine 1 (47.9 mg, 0.330 mmol), cyanoester S3 (109
mg, 0.300 mmol), Pd(OAc)
2 3
(2.0 mg, 0.009 mmol), PPh (4.7 mg, 0.018 mmol) 2,6-
dimethylbenzoquinone (44.9 mg, 0.330 mmol) and N,N-diisopropylethylamine (42.7 mg,
5
1
8.0 µL, 0.660 mmol) in THF (1.5 mL) for 12 h. Purification by flash chromatography (5-
5% EtOAC / hexanes) gave product 7 (103 mg, 0.275 mmol, 92%) as colorless oil. IR:
-
1 1
(
(
7
neat) 2990, 2938, 2892, 1703, 1621, 1581, 1434, 1349, 1242, 1138, 827 cm ; H NMR
400 MHz, CDCl ) δ 7.86 (dd, J = 8.9, 0.5 Hz, 1H), 7.61-7.65 (m, 2H), 7.38-7.45 (m, 3H),
.21-7.24 (m, 5H), 6.58 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.80 (ddd, J = 10.2, 1.1, 0.7
Hz, 1H), 5.68 (ddd, J = 17.4, 1.2, 0.4 Hz, 1H), 4.63 (s, 1H), 3.11 (d, J = 13.3 Hz, 1H),
3
1
3
2
1
4
3
.65 (d, J = 13.3 Hz, 1H), 1.22 (s, 9H) ppm; C NMR (176 MHz, CDCl
3
) δ 166.8, 165.4,
37.3, 136.9, 134.0, 130.3, 129.1, 128.9, 128.7, 128.4, 127.7, 118.2, 84.3, 79.5, 58.6,
0.9, 27.7 ppm; HRMS (ESI+) calcd. for C24
97.1875.
H
26 2 2
N O Na (M+Na) 397.1886, found
NC Me
N
t
O Bu
O
F
8
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-3-(4-fluorophenyl)-2-methylpropanoate
8): The reaction was performed with N-allyl imine S5 (108 mg, 0.660 mmol), cyanoester
(
2
(93.2 mg, 0.600 mmol), Pd(OAc)
2 3
(4.0 mg, 0.018 mmol), PPh (9.4 mg, 0.036 mmol)
2
,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-diisopropylethylamine (85.4
mg, 115 µL, 0.660 mmol) in THF (3.0 mL) for 12 h. Purification by flash chromatography
5-15% EtOAC / hexanes) gave product 8 (162 mg, 0.512 mmol, 85%) as white solid.
Mp. 85-86 ºC; IR: (neat) 2941, 1711, 1621, 1582, 1488, 1352, 1263, 1239, 1142, 1108
(
-
1 1
cm ; H NMR (400 MHz, CDCl
3
) 7.85 (d, J = 8.9 Hz, 1H), 7.47-7.52 (m, 2H), 7.03-7.09
(
(
1
1
m, 2H), 6.56 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.82 (dt, J = 10.2, 0.8 Hz, 1H), 5.68-5.72
1
3
m, 1H), 4.45 (s, 1H), 1.46 (s, 9H), 1.40 (s, 3H) ppm; C NMR (100 MHz, CDCl
3
) δ
67.8, 165.5, 163.0 (d, J = 247.9 Hz), 136.8, 133.1 (d, J = 3.3 Hz), 130.5 (d, J = 7.9 Hz),
29.1, 118.9, 115.5 (d, J = 21.3 Hz), 84.4, 77.8, 51.7 (d, J = 1.3 Hz), 27.9, 21.2 ppm;
HRMS (ESI+) calcd. for C18
H
22FN
2
O
2
(M+H) 317.1660, found 317.1651.
S13

NC Me
N
t
O Bu
O
Cl
9
t-Butyl-3-(((E)-allylidene)amino)-3-(4-chlorophenyl)-2-cyano-2-methylpropanoate
9): The reaction was performed with N-allyl imine S6 (119 mg, 0.660 mmol), cyanoester
(
2
(93.2 mg, 0.600 mmol), Pd(OAc)
2 3
(4.0 mg, 0.018 mmol), PPh (9.4 mg, 0.036 mmol)
2
,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-diisopropylethylamine (85.4
mg, 115 µL, 0.660 mmol) in THF (3.0 mL) for 10 h. Purification by flash chromatography
5-15% EtOAC / hexanes) gave product 9 (186 mg, 0.558 mmol, 93%) as white solid.
Mp. 86-88 ºC; IR: (neat) 2940, 2896, 1711, 1622, 1470, 1351, 1260, 1142, 1108, 823
(
-
1
1
cm ; H NMR (400 MHz, CDCl
3
) δ 7.84 (dd, J = 8.9, 0.3 Hz, 1H), 7.43-7.47 (m, 2H),
7
5
.31-7.34 (m, 2H), 6.55 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.82 (dt, J = 10.3, 0.8 Hz, 1H),
1
3
.70 (ddd, J = 17.4, 1.0, 0.4 Hz, 1H), 4.43 (s, 1H), 1.45 (s, 9H), 1.39 (s, 3H) ppm;
) δ 167.6, 165.6, 136.6, 135.8, 134.6, 130.2, 129.2, 128.7, 118.7,
4.4, 77.7, 51.5, 27.8, 21.1 ppm; HRMS (ESI+) calcd. for C18 (M+H) 333.1364,
found 333.1363.
C
NMR (100 MHz, CDCl
8
3
2 2
H22ClN O
NC Me
N
t
O Bu
O
Br
1
0
t-Butyl-3-(((E)-allylidene)amino)-3-(4-bromophenyl)-2-cyano-2-methylpropanoate
10): The reaction was performed with N-allyl imine S7 (148 mg, 0.660 mmol),
cyanoester 2 (93.2 mg, 0.600 mmol), Pd(OAc) (4.0 mg, 0.018 mmol), PPh (9.4 mg,
.036 mmol) 2,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-
(
2
3
0
diisopropylethylamine (85.4 mg, 115 µL, 0.660 mmol) in THF (3.0 mL) for 12 h.
Purification by flash chromatography (5-15% EtOAC / hexanes) gave product 10 (170
mg, 0.451 mmol, 75%) as colorless oil. IR: (neat) 2939, 1711, 1622, 1581, 1465, 1351,
-
1 1
1
259, 1142, 1108, 996 cm ; H NMR (400 MHz, CDCl
3
) δ 7.84 (d, J = 8.9 Hz, 1H), 7.48-
7
.51 (m, 2H), 7.38-7.41 (m, 2H), 6.55 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.82 (d, J = 10
1
3
Hz, 1H), 5.70 (dd, J = 17.4, 1.1 Hz, 1H), 4.42 (s, 1H), 1.46 (s, 9H), 1.40 (s, 3H) ppm;
C
NMR (100 MHz, CDCl
8
3
3
) δ 167.6, 165.6, 136.7, 136.3, 131.7, 130.5, 129.3, 122.9, 118.7,
4.4, 77.8, 51.5, 27.9, 21.2 ppm; HRMS (ESI+) calcd. for C18 Na (M+Na)
99.0679, found 399.0672.
2 2
H21BrN O
S14

NC Me
N
t
O Bu
O
NO2
11
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-2-methyl-3-(4-nitrophenyl)propanoate
11): The reaction was performed with N-allyl imine S8 (126 mg, 0.660 mmol),
cyanoester 2 (93.2 mg, 0.600 mmol), Pd(OAc) (4.0 mg, 0.018 mmol), PPh (9.4 mg,
.036 mmol) 2,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-
(
2
3
0
diisopropylethylamine (85.4 mg, 115 µL, 0.660 mmol) in THF (3.0 mL) for 10 h.
Purification by flash chromatography (10-25% EtOAC / hexanes) gave product 11 (178
mg, 0.518 mmol, 86%) as white solid. Mp. 122-125 ºC; IR: (neat) 2940, 1711, 1622,
-
1 1
1
581, 1502, 1330, 1263, 1143, 1109, 829 cm ; H NMR (400 MHz, CDCl
3
) δ 8.21-8.24
(
m, 2H), 7.88 (d, J = 8.9 Hz, 1H), 7.70-7.74 (m, 2H), 6.57 (ddd, J = 17.4, 10.2, 8.9 Hz,
1
1
1
H), 5.87 (dt, J = 10.2, 0.8 Hz, 1H), 5.75 (ddd, J = 17.4, 1.0, 0.4 Hz, 1H), 4.56 (s, 1H),
1
3
.47 (s, 9H), 1.42 (s, 3H) ppm; C NMR (100 MHz, CDCl
3
) δ 167.2, 166.3, 148.2, 144.4,
36.5, 130.0, 129.9, 123.7, 118.3, 84.9, 77.7, 51.4, 27.9, 21.2 ppm; HRMS (ESI+) calcd.
for C18
H
21
N
3
O
4
Na (M+Na) 366.1424, found 366.1413.
NC Me
N
t
O Bu
O
O N
2
1
2
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-2-methyl-3-(3-nitrophenyl)propanoate
12): The reaction was performed with N-allyl imine S9 (126 mg, 0.660 mmol),
cyanoester 2 (93.2 mg, 0.600 mmol), Pd(OAc) (4.0 mg, 0.018 mmol), PPh (9.4 mg,
.036 mmol) 2,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-
(
2
3
0
diisopropylethylamine (85.4 mg, 115 µL, 0.660 mmol) in THF (3.0 mL) for 12 h.
Purification by flash chromatography (10-25% EtOAC / hexanes) gave product 12 (171
mg, 0.498 mmol, 83%) as white solid. Mp. 111-113 ºC; IR: (neat) 3048, 2941, 2832,
-
1 1
1
=
9
1
3
710, 1622, 1509, 1331, 1263, 1141, 827 cm ; H NMR (400 MHz, CDCl ) δ 8.30 (dd, J
2.2, 1.8 Hz, 1H), 8.20 (ddd, J = 8.2, 2.3, 1.1 Hz, 1H), 7.96-7.99 (m, 1H), 7.90 (d, J =
.0 Hz, 1H), 7.58 (t, J = 8.0 Hz, 1H), 6.58 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.87 (dt, J =
0.3, 0.8 Hz, 1H), 5.73-5.78 (m, 1H), 4.57 (s, 1H), 1.47 (s, 9H), 1.44 (s, 3H) ppm;
) δ 167.0, 166.4, 148.0, 139.4, 136.5, 135.0, 130.0, 129.7, 123.9,
23.7, 118.4, 84.8, 77.6, 51.5, 27.9, 21.0 ppm; HRMS (ESI+) calcd. for C18
M+H) 344.1605, found 344.1601.
1
3
C
NMR (100 MHz, CDCl
1
(
3
22 3 4
H N O
S15

NC Me
N
t
O Bu
O N
O
2
1
3
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-2-methyl-3-(2-nitrophenyl)propanoate
13): The reaction was performed with N-allyl imine S10 (126 mg, 0.660 mmol),
cyanoester 2 (93.2 mg, 0.600 mmol), Pd(OAc) (4.0 mg, 0.018 mmol), PPh (9.4 mg,
.036 mmol) 2,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-
(
2
3
0
diisopropylethylamine (85.4 mg, 116 µL, 0.660 mmol) in THF (3.0 mL) for 12 h.
Purification by flash chromatography (10-25% EtOAC / hexanes) gave product 13 (194
mg, 0.564 mmol, 94%) as white solid. Mp. 84-86 ºC; IR: (neat) 2940, 1713, 1620, 1509,
-
1 1
1
1
434, 1349, 1260, 1143, 1108, 829 cm ; H NMR (400 MHz, CDCl
3
) δ 8.26 (dd, J = 8.0,
.4 Hz, 1H), 7.95 (d, J = 8.9 Hz, 1H), 7.81 (dd, J = 8.1, 1.3 Hz, 1H), 7.68 (td, J = 7.7, 1.4
Hz, 1H), 7.48 (ddd, J = 8.1, 7.4, 1.4 Hz, 1H), 6.55 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.87
(
(
1
dt, J = 10.3, 0.8 Hz, 1H), 5.77 (dd, J = 17.4, 0.6 Hz, 1H), 5.40 (s, 1H), 1.46 (s, 9H), 1.38
1
3
s, 3H) ppm; C NMR (100 MHz, CDCl
31.3, 130.0, 129.3, 124.1, 118.8, 84.7, 70.0, 52.3, 20.9 ppm; HRMS (ESI+) calcd. for
(M+H) 344.1605, found 344.1596.
3
) δ 167.03, 167.00, 150.0, 136.6, 133.2, 131.4,
18 22 3 4
C H N O
NC Me
N
t
O Bu
O
CF3
1
4
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-2-methyl-3-(4-(trifluoromethyl)phenyl)-
propanoate (14): The reaction was performed with N-allyl imine S11 (141 mg, 0.660
mmol), cyanoester 2 (93.2 mg, 0.600 mmol), Pd(OAc) (4.0 mg, 0.018 mmol), PPh (9.4
2 3
mg, 0.036 mmol) 2,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-
diisopropylethylamine (85.4 mg, 116 µL, 0.660 mmol) in THF (3.0 mL) for 18 h.
Purification by flash chromatography (5-15% EtOAC / hexanes) gave product 14 (174
mg, 0.474 mmol, 79%) as colorless oil. IR: (neat) 2940, 1710, 1618, 1505, 1440, 1348,
-
1 1
1
7
5
262, 1145, 1110, 827 cm ; H NMR (400 MHz, CDCl
3
) δ 7.87 (dd, J = 8.9, 0.4 Hz, 1H),
.62-7.67 (m, 4H), 6.57 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.85 (dt, J = 10.3, 0.9 Hz, 1H),
.72 (ddd, J = 17.4, 1.0, 0.4 Hz, 1H), 4.52 (s, 1H), 1.47 (s, 9H), 1.42 (s, 3H) ppm;
1
3
C
NMR (100 MHz, CDCl
3
) δ 167.5, 166.0, 141.3, 136.6, 130.9 (q, J = 32.2 Hz), 129.5,
1
29.4, 125.5 (q, J = 3.7 Hz), 124.1 (q, J = 271 Hz), 118.6, 84.6, 78.0, 51.5, 27.9, 21.2
ppm.
S16

NC Me
N
t
O Bu
O
Me
1
5
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-2-methyl-3-(p-tolyl)propanoate (15): The
reaction was performed with N-allyl imine S12 (105 mg, 0.660 mmol), cyanoester 2 (93.2
mg, 0.600 mmol), Pd(OAc)
2 3
(4.0 mg, 0.018 mmol), PPh (9.4 mg, 0.036 mmol) 2,6-
dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-diisopropylethylamine (85.4 mg,
1
1
1
16 µL, 0.660 mmol) in THF (3.0 mL) for 14 h. Purification by flash chromatography (5-
5% EtOAC / hexanes) gave product 15 (178 mg, 0.570 mmol, 95%) as white solid. Mp.
02-104 ºC; IR: (neat) 2939, 2897, 1711, 1621, 1435, 1351, 1262, 1142, 1108, 829 cm ;
-
1
1
H NMR (400 MHz, CDCl
3
) δ 7.85 (dd, J = 8.9, 0.5 Hz, 1H), 7.38-7.41 (m, 2H), 7.16-7.18
(
m, 2H), 6.57 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.79 (dt, J = 10.2, 0.9 Hz, 1H), 5.67 (ddd,
1
3
J = 17.4, 1.1, 0.4 Hz, 1H), 4.43 (s, 1H), 2.34 (s, 3H), 1.47 (s, 9H), 1.41 (s, 3H) ppm;
NMR (100 MHz, CDCl ) δ 168.0, 165.2, 138.6, 137.0, 134.3, 129.3, 128.8, 128.7, 119.1,
4.2, 78.4, 51.7, 27.9, 21.3, 21.2 ppm; HRMS (ESI+) calcd. for C19 (M+H)
13.1911, found 313.1906.
C
3
8
3
25 2 2
H N O
NC Me
N
t
O Bu
O
OMe
1
6
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-3-(4-methoxyphenyl)-2-methylpropanoate
16): The reaction was performed with N-allyl imine S13 (116 mg, 0.660 mmol),
cyanoester 2 (93.2 mg, 0.600 mmol), Pd(OAc) (4.0 mg, 0.018 mmol), PPh (9.4 mg,
.036 mmol) 2,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-
(
2
3
0
diisopropylethylamine (85.4 mg, 116 µL, 0.660 mmol) in THF (3.0 mL) for 16 h.
Purification by flash chromatography (10-20% EtOAC / hexanes) gave product 16 (176
mg, 0.536 mmol, 89%) as white solid. Mp. 73-75 ºC; IR: (neat) 2939, 2896, 1710, 1584,
-
1 1
1
491, 1351, 1235, 1144, 1108, 826 cm ; H NMR (400 MHz, CDCl
3
) δ 7.84 (d, J = 8.9
Hz, 1H), 7.41-7.45 (m, 2H), 6.88-6.91 (m, 2H), 6.57 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H),
5
1
1
.79 (dt, J = 10.3, 0.8 Hz, 1H), 5.65-5.70 (m, 1H), 4.42 (s, 1H), 3.80 (s, 3H), 1.47 (s, 9H),
1
3
.40 (s, 3H) ppm; C NMR (100 MHz, CDCl
3
) δ 168.0, 165.1, 159.9, 136.9, 130.0,
29.4, 128.7, 119.2, 113.9, 84.1, 78.1, 55.4, 51.8, 27.9, 21.2 ppm; HRMS (ESI+) calcd.
for C19
H
24
N
2
O
3
Na (M+Na) 351.1679, found 351.1675.
S17

NC Me
N
t
O Bu
O
1
7
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-2-methyl-3-(naphthalen-1-yl)propanoate
17): The reaction was performed with N-allyl imine S14 (129 mg, 0.660 mmol),
cyanoester 2 (93.2 mg, 0.600 mmol), Pd(OAc) (4.0 mg, 0.018 mmol), PPh (9.4 mg,
.036 mmol) 2,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-
(
2
3
0
diisopropylethylamine (85.4 mg, 116 µL, 0.660 mmol) in THF (3.0 mL) for 16 h.
Purification by flash chromatography (5-15% EtOAC / hexanes) gave product 17 (189
mg, 0.542 mmol, 90%) as white solid. Mp. 114-116 ºC; IR: (neat) 3012, 2939, 1709,
-
1 1
1
621, 1580, 1434, 1351, 1258, 1144, 1108 cm ; H NMR (400 MHz, CDCl
J = 19.8, 7.9 Hz, 2H), 7.93 (dd, J = 8.9, 0.4 Hz, 1H), 7.84-7.89 (m, 2H), 7.50-7.59 (m,
H), 6.60 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.80 ((dt, J = 10.2, 0.8 Hz, 1H)), 5.64-5.68
3
) δ 8.18 (dd,
3
(
1
1
1
3
m, 1H), 5.57 (s, 1H), 1.51 (s, 9H), 1.36 (s, 3H) ppm; C NMR (100 MHz, CDCl
3
) δ
68.6, 165.3, 137.0, 133.8, 133.5, 132.1, 129.5, 129.0, 128.9, 127.9, 126.6, 126.0,
25.7, 122.7, 119.3, 84.5, 71.3, 53.3, 28.0, 21.8 ppm; HRMS (ESI+) calcd. for
(M+H) 349.1911, found 349.1903.
22 25 2 2
C H N O
NC Me
N
t
O Bu
O
1
8
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-2-methyl-3-(naphthalen-2-yl)propanoate
18): The reaction was performed with N-allyl imine S15 (129 mg, 0.660 mmol),
cyanoester 2 (93.2 mg, 0.600 mmol), Pd(OAc) (4.0 mg, 0.018 mmol), PPh (9.4 mg,
.036 mmol) 2,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-
(
2
3
0
diisopropylethylamine (85.4 mg, 116 µL, 0.660 mmol) in THF (3.0 mL) for 14 h.
Purification by flash chromatography (5-15% EtOAC / hexanes) gave product 18 (171
mg, 0.491 mmol, 82%) as white solid. Mp. 96-98 ºC; IR: (neat) 3014, 2939, 2896, 1710,
-
1 1
1
(
6
620, 1582, 1351, 1241, 1142, 828 cm ; H NMR (400 MHz, CDCl
d, J = 11.2 Hz, 1H), 7.82-7.89 (m, 3H), 7.70 (dd, J = 8.6, 1.7 Hz, 1H), 7.47-7.51 (m, 2H),
.62 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.82 (d, J = 10.2 Hz, 1H), 5.70 (dd, J = 17.4, 0.9
3
) δ 7.93 (s, 1H), 7.92
1
3
Hz, 1H), 4.66 (s, 1H), 1.50 (s, 9H), 1.46 (s, 3H) ppm; C NMR (176 MHz, CDCl
3
) δ
68.0, 165.6, 136.9, 134.8, 133.5, 133.1, 129.0, 128.35, 128.34, 128.28, 127.8, 126.5,
26.4, 126.3, 119.1, 84.3, 78.7, 51.7, 27.9, 21.3 ppm; HRMS (ESI+) calcd. for
1
1
C
22
H
25
N
2
O
2
(M+H) 349.1911, found 349.1908.
S18

NC Me
N
t
O Bu
O
O
1
9
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-3-(furan-2-yl)-2-methylpropanoate
The reaction was performed with N-allyl imine S16 (89.2 mg, 0.660 mmol), cyanoester 2
93.2 mg, 0.600 mmol), Pd(OAc) (4.0 mg, 0.018 mmol), PPh (9.4 mg, 0.036 mmol) 2,6-
dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-diisopropylethylamine (85.4 mg,
(19):
(
2
3
1
2
16 µL, 0.660 mmol) in THF (3.0 mL) for 18 h. Purification by flash chromatography (10-
0% EtOAC / hexanes) gave product 19 (151 mg, 0.524 mmol, 87%) as colorless oil. IR:
-
1
1
(
neat) 2940, 1711, 1624, 1583, 1352, 1259, 1142, 1107, 992, 829 cm ; H NMR (400
MHz, CDCl ) δ 7.85 (dd, J = 8.9, 0.6 Hz, 1H), 7.42 (dd, J = 1.8, 0.9 Hz, 1H), 6.56 (ddd, J
17.4, 10.2, 8.9 Hz, 1H), 6.49 (dt, J = 3.3, 0.7 Hz, 1H), 6.38-6.39 (m, 1H), 5.84 (dt, J =
0.2, 0.9 Hz, 1H), 5.73 (ddd, J = 17.4, 1.1, 0.4 Hz, 1H), 4.75 (s, 1H), 1.51 (s, 3H), 1.47
3
=
1
1
3
(
1
s, 9H) ppm; C NMR (100 MHz, CDCl
19.0, 110.8, 109.7, 84.4, 71.8, 50.9, 27.9, 20.4 ppm; HRMS (ESI+) calcd. for
(M+H) 289.1547, found 289.1546.
3
) δ 167.2, 166.4, 150.3, 142.8, 136.7, 129.5,
16 21 2 3
C H N O
NC Me
N
t
O Bu
O
N
2
0
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-2-methyl-3-(pyridin-4-yl)propanoate (20):
The reaction was performed with N-allyl imine S17 (96.5 mg, 0.660 mmol), cyanoester 2
(
93.2 mg, 0.600 mmol), Pd(OAc)
2 3
(4.0 mg, 0.018 mmol), PPh (9.4 mg, 0.036 mmol) 2,6-
dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-diisopropylethylamine (85.4 mg,
1
8
1
16 µL, 0.660 mmol) in THF (3.0 mL) for 16 h. Purification by flash chromatography (40-
0% EtOAC / hexanes) gave product 20 (154 mg, 0.514 mmol, 86%) as white solid. Mp.
33-135 ºC; IR: (neat) 2940, 1711, 1621, 1578, 1393, 1351, 1243, 1143, 1109, 828 cm ;
-
1
1
H NMR (400 MHz, CDCl
3
) δ 8.61 (dd, J = 6.4, 2.8 Hz, 2H), 7.86 (d, J = 8.9 Hz, 1H), 7.43
(
dd, J = 6.4, 2.8 Hz, 2H), 6.56 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.86 (dt, J = 10.3, 0.8
1
3
Hz, 1H), 5.73 (dd, J = 17.4, 1.0 Hz, 1H), 4.42 (s, 1H), 1.46 (s, 9H), 1.42 (s, 3H) ppm;
NMR (100 MHz, CDCl ) δ 167.2, 166.3, 150.1, 145.8, 136.5, 129.8, 123.8, 118.3, 84.8,
7.4, 51.2, 27.9, 21.1 ppm; HRMS (ESI+) calcd. for C17 (M+H) 300.1707, found
00.1708.
C
3
7
3
22 3 2
H N O
NC Me
N
t
O Bu
O
NSO Ph
2
2
1
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-2-methyl-3-(1-(phenylsulfonyl)-1H-indol-3-
yl)propanoate (21): The reaction was performed with N-allyl imine S18 (214 mg, 0.660
mmol), cyanoester 2 (93.2 mg, 0.600 mmol), Pd(OAc) (4.0 mg, 0.018 mmol), PPh (9.4
2 3
mg, 0.036 mmol) 2,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-
S19

diisopropylethylamine (85.4 mg, 116 µL, 0.660 mmol) in THF (3.0 mL) for 15 h.
Purification by flash chromatography (20-40% EtOAC / hexanes) gave product 21 (232
mg, 0.486 mmol, 81%) as white gum. IR: (neat) 2940, 1711, 1622, 1581, 1427, 1352,
-
1 1
1
7
7
1
0
1
1
3
262, 1162, 1104, 828 cm ; H NMR (400 MHz, CDCl ) δ 8.01 (dt, J = 8.3, 0.9 Hz, 1H),
.91-7.94 (m, 2H), 7.89 (s, 1H), 7.86 (d, J = 8.9 Hz, 1H), 7.66 (dt, J = 7.8, 0.9 Hz, 1H),
.50-7.54 (m, 1H), 7.41-7.45 (m, 2H), 7.33 (ddd, J = 8.3, 7.2, 1.2 Hz, 1H), 7.23-7.27 (m,
H), 6.58 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.83 (d, J = 10.3 Hz, 1H), 5.68 (dd, J = 17.4,
.7 Hz, 1H), 4.84 (s, 1H), 1.47 (s, 9H), 1.38 (s, 3H) ppm; C NMR (100 MHz, CDCl ) δ
3
67.6, 165.5, 137.8, 136.6, 134.7, 134.0, 130.0 129.4, 129.3, 127.1, 126.1, 125.2, 123.6,
20.2, 119.3, 119.2, 114.0, 84.4, 70.7, 52.6, 27.9, 21.4 ppm; HRMS (ESI+) calcd. for
1
3
C
26
H
27
N
3
O
4
SNa (M+Na) 500.1614, found 500.1606.
NC Me
N
t
O Bu
O
2
2
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-3-(cyclohex-1-en-1-yl)-2-
methylpropanoate (22): The reaction was performed with N-allyl imine S19 (98.5 mg,
0
.660 mmol), cyanoester 2 (93.2 mg, 0.600 mmol), Pd(OAc)
2
(4.0 mg, 0.018 mmol),
PPh (9.4 mg, 0.036 mmol) 2,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-
3
diisopropylethylamine (85.4 mg, 116 µL, 0.660 mmol) in THF (3.0 mL) for 18 h.
Purification by flash chromatography (5-15% EtOAC / hexanes) gave product 22 (137
mg, 0.453 mmol, 75%) as white solid. Mp. 93-95 ºC; IR: (neat) 2939, 2892, 1711, 1620,
-
1 1
1
0
5
1
1
2
3
433, 1352, 1240, 1144, 1102, 828 cm ; H-NMR (400 MHz; CDCl ): δ 7.79 (dd, J = 8.9,
.5 Hz, 1H), 6.55 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.80 (dt, J = 10.2, 0.9 Hz, 1H), 5.75-
.77 (m, 1H), 5.67-5.71 (m, 1H), 3.79 (s, 1H), 2.14-2.33 (m, 2H), 2.04-2.07 (m, 2H),
1
3
.52-1.73 (m, 4H), 1.50 (s, 3H), 1.44 (s, 9H) ppm; C NMR (100 MHz, CDCl
64.5, 137.1, 135.1, 129.1, 128.3, 120.2, 83.9, 81.4, 49.1, 27.9, 25.7, 25.5, 22.7, 22.4,
1.3 ppm; HRMS (ESI+) calcd. for C18 Na (M+Na) 325.1886, found 325.1885.
3
) δ 168.3,
26 2 2
H N O
NC Me
N
t
O Bu
O
2
3
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-3-(cyclopent-1-en-1-yl)-2-
methylpropanoate (23): The reaction was performed with N-allyl imine S20 (89.3 mg,
0
.660 mmol), cyanoester 2 (93.2 mg, 0.600 mmol), Pd(OAc)
2
(4.0 mg, 0.018 mmol),
PPh (9.4 mg, 0.036 mmol) 2,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-
3
diisopropylethylamine (85.4 mg, 116 µL, 0.660 mmol) in THF (3.0 mL) for 17 h.
Purification by flash chromatography (5-15% EtOAC / hexanes) gave product 23 (152
mg, 0.527 mmol, 88%) as colorless oil. IR: (neat) 2938, 1711, 1622, 1582, 1434, 1351,
-
1 1
1
6
257, 1144, 1103, 929 cm ; H-NMR (400 MHz; CDCl
3
): δ 7.79 (dd, J = 8.9, 0.6 Hz, 1H),
.55 (ddd, J = 17.4, 10.2, 8.9 Hz, 1H), 5.78-5.81 (m, 2H), 5.69 (ddd, J = 17.4, 0.8, 0.4
Hz, 1H), 4.16 (s, 1H), 2.54-2.63 (m, 1H), 2.36-2.44 (m, J = 9.3 Hz, 1H), 2.30-2.36 (m,
1
3
2
3
H), 1.78-1.96 (m, 2H), 1.51 (s, 3H), 1.44 (s, 9H) ppm; C NMR (100 MHz, CDCl ) δ
S20

1
2
68.0, 164.8, 140.4, 137.0, 131.9, 128.5, 120.0, 84.0, 75.6, 49.3, 32.4, 31.9, 27.9, 23.5,
1.0 ppm; HRMS (ESI+) calcd. for C17 (M+H) 289.1911, found 289.1909.
25 2 2
H N O
NC Me
N
t
O Bu
O
2
4
t-Butyl-3-(((E)-allylidene)amino)-2-cyano-3-cyclohexyl-2-methylpropanoate
The reaction was performed with N-allyl imine S21 (99.8 mg, 0.660 mmol), cyanoester 2
93.2 mg, 0.600 mmol), Pd(OAc) (4.0 mg, 0.018 mmol), PPh (9.4 mg, 0.036 mmol) 2,6-
dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-diisopropylethylamine (85.4 mg,
(24):
(
2
3
1
1
9
16 µL, 0.660 mmol) in THF (3.0 mL) for 60 h. Purification by flash chromatography (5-
5% EtOAC / hexanes) gave product 24 (102 mg, 0.335 mmol, 56%) as white solid. Mp.
3-95 ºC; IR: (neat) 2886, 2813, 1705, 1623, 1581, 1429, 1350, 1240, 1142, 942 cm ;
-
1
1
H NMR (400 MHz, CDCl
3
) δ 7.71 (d, J = 8.9 Hz, 1H), 6.54 (ddd, J = 17.4, 10.2, 8.9 Hz,
H), 5.81 (ddd, J = 10.2, 1.0, 0.8 Hz, 1H), 5.69-5.73 (m, 1H), 3.10 (d, J = 4.1 Hz, 1H),
.00-2.04 (m, 1H), 1.70-1.81 (m, 3H), 1.59 (s, 3H), 1.49-1.53 (m, 1H), 1.43 (s, 9H), 1.14-
1
2
1
1
1
3
.33 (m, 2H), 0.95-1.12 (m, 2H) ppm; C NMR (100 MHz, CDCl
28.5, 120.1, 83.9, 79.6, 49.0, 39.2, 32.1, 28.2, 27.8, 26.5, 26.3, 26.1, 20.3 ppm; HRMS
(M+H) 305.2224, found 305.2222.
3
) δ 167.9, 165.0, 136.7,
(
ESI+) calcd. for C18
H
29
N
2
O
2
Test of Diastereoselectivity for Imine addition by Lewis Acid Activation:
NC Me
t
O
BocHN
O Bu
NBoc
Cu(OTf)2
NC
+
O
O
Hünig's base
THF
Ph
Me
2
S24
t-Butyl 3-((t-butoxycarbonyl)amino)-2-cyano-2-methyl-3-phenylpropanoate (S24):
To a stirred solution of N-boc phenyl imine (67.8 mg, 0.330 mmol, 1.1 equiv.) and
cyanoester 2 (46.6 mg, 0.300 mmol, 1.0 equiv.) in THF (1.5 mL) was added Cu(OTf)
10.9 mg,0.030 mmol, 0.10 equiv.) followed by N,N-diisopropylethylamine (58 µL, 42.6
mg, 0.330 mmol, 1.1 equiv.). After 2.5 h, the reaction was quenched with satd. aq.
NaHCO (5 mL) and the aqueous layer was extracted with Et O (2 X 10 mL). The dried
extract (MgSO ) was concentrated in vacuo and was purified by flash chromatography
2
(
3
2
4
over silica gel, eluting with 10-20% EtOAC / hexanes to give coupled adduct S24 (72.1
mg, 0.200 mmol, 67%) as colorless oil in 1:1 dr.
General Method for Synthesis of 2-Aza Diene via Oxidative C-H Activation:
Pd(OAc)2
PPh3
O
NC
Ph
+
R
N
t
t
Hünig's base
R
N
O Bu
CO Bu
2
Ph
CN
2,6-DMBQ
2
5
THF, rt
An oven dried Pyrex microwave vial was charged with Pd(OAc)
2
(0.05 equiv.), PPh
3
(
0.10 equiv.), 2,6-dimethylbenzoquinone (1.1 equiv.) and was sealed with a rubber
S21

septa. The vial was evacuated and filled with nitrogen three times in an interval of 10
min. In a separate sealed nitrogen flushed vial, cyanoester 25 (1.0 equiv.) and N-allyl
imine (1.1 equiv.) were taken in freshly distilled THF. The solution was cannulated to the
microwave vial with palladium catalyst. N,N-diisopropylethylamine (1.1 equiv.) was
added to the resulting turbid solution and was allowed to stir at rt for 48-65 h depending
on the substrates. Upon completion (monitored by crude NMR), the reaction was passed
through a plug of silica gel (pre-neutralized with 2% Et
3
N in Hexanes). Solvent was
removed in vacuo and the residue was purified by flash chromatography over silica gel
(
pre-neutralized with 1% Et
3
N in Hexanes), eluting with EtOAc / hexanes, to give 2-aza-
dienes 26-31.
O
t
N
O Bu
Ph
CN
2
6
t-Butyl-(E)-5-(((E)-benzylidene)amino)-2-cyano-2-phenylpent-4-enoate (26): The
reaction was performed with N-allyl imine 1 (145 mg, 1.10 mmol), cyanoester 25 (217
mg, 1.00 mmol), Pd(OAc)
2 3
(11.2 mg, 0.050 mmol), PPh (26.2 mg, 0.100 mmol), 2,6-
dimethylbenzoquinone (150 mg, 1.10 mmol) and N,N-diisopropylethylamine (142 mg,
0
1
.19 mL, 1.10 mmol) in THF (5.0 mL) for 52 h. Purification by flash chromatography (5-
5% EtOAC / hexanes) gave product 26 (175 mg, 0.485 mmol, 81%) as colorless oil. IR:
-
1
1
(
neat) 2937, 2892, 1712, 1578, 1550, 1429, 1351, 1236, 1136, 826 cm ; H-NMR (400
MHz; CDCl ): δ 8.21 (s, 1H), 7.76-7.78 (m, 2H), 7.56-7.58 (m, 2H), 7.35-7.44 (m, 6H),
.97 (d, J = 12.9 Hz, 1H), 6.04 (dt, J = 12.9, 7.8 Hz, 1H), 3.20 (ddd, J = 14.1, 8.2, 1.0 Hz,
3
6
1
1
3
3
H), 2.94 (ddd, J = 14.1, 7.5, 1.1 Hz, 1H), 1.43 (s, 9H) ppm; C NMR (100 MHz, CDCl )
δ 166.0, 162.0, 147.4, 135.9, 134.6, 131.4, 129.2, 128.9, 128.81, 128.79, 126.2, 123.8,
18.4, 84.7, 55.3, 39.2, 27.7 ppm; HRMS (ESI+) calcd. for C23 (M+H) 361.1911,
found 361.1906.
1
25 2 2
H N O
O
t
N
O Bu
Ph
CN
Cl
2
7
t-Butyl-(E)-5-(((E)-4-chlorobenzylidene)amino)-2-cyano-2-phenylpent-4-enoate (27):
The reaction was performed with N-allyl imine S6 (119 mg, 0.660 mmol), cyanoester 25
(
2
130 mg, 0.600 mmol), Pd(OAc)
,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-diisopropylethylamine (85.3
mg, 115 µL, 0.660 mmol) in THF (3.0 mL) for 48 h. Purification by flash chromatography
5-15% EtOAC / hexanes) gave product 27 (199 mg, 0.504 mmol, 84%) as colorless oil.
2 3
(6.7 mg, 0.030 mmol), PPh (15.7 mg, 0.060 mmol),
(
-
1
IR: (neat) 2939, 2893, 1713, 1568, 1469, 1351, 1237, 1136, 1073, 825 cm ; 1H-NMR
400 MHz; CDCl3): δ 8.15 (s, 1H), 7.68-7.72 (m, 2H), 7.55-7.57 (m, 2H), 7.35-7.44 (m,
(
5
1
H), 6.95 (d, J = 12.9 Hz, 1H), 6.04 (dt, J = 12.9, 7.8 Hz, 1H), 3.20 (ddd, J = 14.1, 8.1,
1
3
.0 Hz, 1H), 2.93 (ddd, J = 14.1, 7.6, 1.1 Hz, 1H), 1.43 (s, 9H) ppm; C NMR (100 MHz,
) δ 165.9, 160.4, 147.1, 137.3, 134.5, 134.4, 129.9, 129.2, 129.1, 128.9, 126.1,
24.5, 118.4, 84.7, 55.2, 39.1, 27.7 ppm; HRMS (ESI+) calcd. for C23 (M+H)
95.1521, found 395.1515.
CDCl
1
3
3
2 2
H24ClN O
S22

O
t
N
O Bu
Ph
CN
Me
2
8
t-Butyl-(E)-2-cyano-5-(((E)-4-methylbenzylidene)amino)-2-phenylpent-4-enoate
28): The reaction was performed with N-allyl imine S12 (105 mg, 0.660 mmol),
cyanoester 25 (130 mg, 0.600 mmol), Pd(OAc) (6.7 mg, 0.030 mmol), PPh (15.7 mg,
.060 mmol), 2,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-
(
2
3
0
diisopropylethylamine (85.4 mg, 116 µL, 0.660 mmol) in THF (3.0 mL) for 55 h.
Purification by flash chromatography (5-15% EtOAC / hexanes) gave product 28 (201
mg, 0.537 mmol, 89%) as colorless oil. IR: (neat) 2938, 2890, 1712, 1573, 1543, 1351,
-
1
1
1
2
1
1
1
1
3
3
236, 1136, 825 cm ; H NMR (400 MHz; CDCl ): δ 8.17 (s, 1H), 7.66 (d, J = 8.1 Hz,
H), 7.56-7.58 (m, 2H), 7.35-7.44 (m, 3H), 7.22 (d, J = 8.0 Hz, 2H), 6.95 (d, J = 13.0 Hz,
H), 6.01 (dt, J = 13.0, 7.8 Hz, 1H), 3.20 (ddd, J = 14.1, 8.2, 0.9 Hz, 1H), 2.93 (ddd, J =
4.1, 7.5, 1.1 Hz, 1H), 2.38 (s, 3H), 1.43 (s, 9H) ppm; C NMR (100 MHz, CDCl
66.0, 162.0, 147.6, 141.9, 134.6, 133.3, 129.6, 129.2, 128.9, 128.8, 126.2, 123.1,
18.5, 84.6, 55.3, 39.2, 27.7, 21.7 ppm; HRMS (ESI+) calcd. for C24
75.2067, found 375.2062.
1
3
3
) δ
27 2 2
H N O (M+H)
O
t
N
O Bu
Ph
TMS
CN
2
9
t-Butyl-(E)-2-cyano-2-phenyl-5-(((E)-2-(4-(trimethylsilyl)but-3-yn-1-
yl)benzylidene)amino)pent-4-enoate (29): The reaction was performed with N-allyl
imine S23 (178 mg, 0.660 mmol), cyanoester 25 (130 mg, 0.600 mmol), Pd(OAc) (6.7
mg, 0.030 mmol), PPh (15.7 mg, 0.060 mmol), 2,6-dimethylbenzoquinone (89.8 mg,
.660 mmol) and N,N-diisopropylethylamine (85.4 mg, 116 mL, 0.660 mmol) in THF (3.0
2
3
0
mL) for 60 h. Purification by flash chromatography (5-15% EtOAC / hexanes) gave
product 29 (219 mg, 0.452 mmol, 75%) as colorless oil. IR: (neat) 2918, 2861, 2143,
-
1
1
1
1
7
1
7
3
713, 1564, 1429, 1351, 1234, 1136, 829 cm ; H-NMR (400 MHz; CDCl ): δ 8.51 (s,
H), 7.96 (dd, J = 7.8, 1.5 Hz, 1H), 7.56-7.58 (m, 2H), 7.36-7.45 (m, 3H), 7.34 (dd, J =
.4, 1.6 Hz, 1H), 7.22-7.29 (m, 2H), 6.99 (d, J = 12.9 Hz, 1H), 6.04 (dt, J = 12.9, 7.8 Hz,
H), 3.20 (ddd, J = 14.1, 8.1, 0.9 Hz, 1H), 3.08 (t, J = 7.5 Hz, 2H), 2.94 (ddd, J = 14.1,
.6, 1.1 Hz, 1H), 2.49 (t, J = 7.5 Hz, 2H), 1.44 (s, 9H), 0.12 (s, 9H) ppm; C NMR (100
) δ 166.0, 160.0, 147.9, 141.0, 134.6, 133.6, 131.0, 130.7, 129.2, 128.9,
28.4, 127.0, 126.2, 123.9, 118.5, 106.0, 86.0, 84.7, 55.3, 39.3, 31.8, 27.8, 22.4, 0.19
1
3
MHz, CDCl
1
3
ppm; HRMS (ESI+) calcd. for C30
H
37
N
2
O
2
Si (M+H) 485.2619, found 485.2604.
O
t
N
O Bu
Ph
CN
N
3
0
t-Butyl-(E)-2-cyano-2-phenyl-5-(((E)-pyridin-4-ylmethylene)amino)pent-4-enoate
(
30): The reaction was performed with N-allyl imine S17 (96.5 mg, 0.660 mmol),
S23

cyanoester 25 (130 mg, 0.600 mmol), Pd(OAc)
2 3
(6.7 mg, 0.030 mmol), PPh (15.8 mg,
0
.060 mmol), 2,6-dimethylbenzoquinone (89.8 mg, 0.660 mmol) and N,N-
diisopropylethylamine (85.4 mg, 116 mL, 0.660 mmol) in THF (3.0 mL) for 54 h.
Purification by flash chromatography (40-80% EtOAC / hexanes) gave product 30 (155
mg, 0.429 mmol, 71%) as colorless oil. IR: (neat) 2938, 2893, 1713, 1576, 1430, 1393,
-
1 1
1
8
351, 1237, 1136, 964 cm ; H-NMR (400 MHz; CDCl
3
): δ 8.68 (dd, J = 6.4, 2.8 Hz, 2H),
.15 (s, 1H), 7.61 (dd, J = 6.4, 2.8 Hz, 2H), 7.54-7.56 (m, 2H), 7.35-7.44 (m, 3H), 6.99
(
d, J = 12.8 Hz, 1H), 6.15 (dt, J = 12.9, 7.7 Hz, 1H), 3.21 (ddd, J = 14.1, 8.1, 1.0 Hz, 1H),
1
3
2
1
5
3
.95 (ddd, J = 14.1, 7.6, 1.1 Hz, 1H), 1.42 (s, 9H) ppm; C NMR (100 MHz, CDCl
3
) δ
65.8, 159.4, 150.6, 146.7, 142.7, 134.4, 129.3, 129.0, 127.2, 126.1, 122.2, 118.3, 84.8,
5.1, 39.1, 27.7 ppm; HRMS (ESI+) calcd. for C22
62.1865.
24 3 2
H N O (M+H) 362.1863, found
O
t
N
O Bu
Ph
CN
3
1
t-Butyl-(E)-2-cyano-5-(((E)-cyclohex-1-en-1-ylmethylene)amino)-2-phenylpent-4-
enoate (31): The reaction was performed with N-allyl imine S19 (164 mg, 1.10 mmol),
cyanoester 25 (217 mg, 1.00 mmol), Pd(OAc)
2 3
(11.3 mg, 0.050 mmol), PPh (26.3 mg,
0
.100 mmol), 2,6-dimethylbenzoquinone (150 mg, 1.10 mmol) and N,N-
diisopropylethylamine (142 mg, 0.19 mL, 1.10 mmol) in THF (5.0 mL) for 65 h.
Purification by flash chromatography (5-15% EtOAC / hexanes) gave product 31 (283
mg, 0.776 mmol, 78%) as colorless oil. IR: (neat) 2937, 2890, 2819, 1713, 1562, 1429,
-
1
1
1
2
7
2
3
351, 1236, 1136, 827 cm ; H-NMR (400 MHz; CDCl ): δ 7.73 (s, 1H), 7.53-7.55 (m,
H), 7.33-7.42 (m, 3H), 6.78 (d, J = 13.0 Hz, 1H), 6.25-6.27 (m, 1H), 5.86 (dt, J = 13.0,
.8 Hz, 1H), 3.13 (ddd, J = 14.1, 8.1, 0.9 Hz, 1H), 2.88 (ddd, J = 14.1, 7.5, 1.0 Hz, 1H),
.28-2.30 (m, 2H), 2.22-2.24 (m, 2H), 1.64 (dt, J = 6.2, 3.0 Hz, 4H), 1.41 (s, 9H) ppm;
1
3
C NMR (100 MHz, CDCl
26.2, 121.7, 118.5, 84.5, 55.3, 39.2, 27.7, 26.6, 23.7, 22.4, 22.0 ppm; HRMS (ESI+)
(M+H) 365.2224, found 365.2220.
3
) δ 166.0, 165.7, 148.0, 142.0, 138.3, 134.6, 129.1, 128.8,
1
29 2 2
calcd. for C23H N O
General Method for Synthesis of Pyridine Derivatives:
X
X
O
1
) MrBr , C H
O
2
6 6
OEt 2) Pd/C, reflux
+
N
N
OEt
N
O
Ph
tBuO
Ph CN
32
CN
An oven dried round bottom flask was charged with 2-aza-diene (1.0 equiv.), enamine
1
5
ester 32 (2.0 equiv.), MgBr
and filled with argon (X 3). Toluene was added to the mixture and warmed to 60 ºC. After
4 h, Pd/C (5 wt. %) was added and heated to reflux. After 10 h, the reaction was cooled
2
(1.2 equiv.), and 4 Å mol. sieves. The flask was evacuated
2
down to rt. The reaction mixture was directly loaded onto column and purified by flash
S24

chromatography over silica gel, eluting with 20-40% EtOAc / hexanes, to give hetero
biaryl systems 33 and 34.
O
N
OEt
Ph
CN
3
3
Ethyl 5-(2-cyano-2-phenylethyl)-2-phenylnicotinate (33): The first step was perform-
ed with 2-aza-diene 26 (32.7 mg, 0.091 mmol, 1.0 equiv.), enamine ester 32 (30.7 mg,
0
(
.181 mmol, 2.0 equiv.), MgBr
50 mg) in toluene (1.0 mL). The second step was performed in the same pot by the
addition of Pd/C (40 mg, 5 wt. %). Purification by flash chromatography (20-40% EtOAC
2
(40.1 mg, 0.219 mmol, 2.4 equiv.), and 4 Å mol. Sieves
/
3
hexanes) gave product 33 (19.3 mg, 0.054 mmol, 59%) as colorless oil. IR: (neat)
-
1 1
017, 2988, 2940, 1698, 1578, 1428, 1269, 1202, 1082, 1004 cm ; H NMR (400 MHz;
): δ 8.46 (d, J = 2.3 Hz, 1H), 7.85 (d, J = 2.3 Hz, 1H), 7.50-7.53 (m, 2H), 7.36-7.43
m, 6H), 7.28-7.31 (m, 2H), 4.15 (q, J = 7.1 Hz, 2H), 4.10 (t, J = 7.2 Hz, 1H), 3.22-3.32
CDCl
(
(
1
3
3
1
3
m, 2H), 1.05 (t, J = 7.2 Hz, 3H) ppm; C NMR (100 MHz, CDCl
3
) δ 167.9, 158.1, 151.8,
39.8, 138.6, 134.2, 129.8, 129.5, 128.8, 128.7, 128.3, 127.6, 127.1, 119.7, 61.8, 39.2,
8.7, 13.8 ppm; HRMS (ESI+) calcd. for C23 (M+H) 357.1598, found 357.1601.
21 2 2
H N O
Cl
O
N
OEt
Ph
CN
3
4
Ethyl 2-(4-chlorophenyl)-5-(2-cyano-2-phenylethyl)nicotinate (34): The first step was
performed with 2-aza-diene 27 (62.5 mg, 0.158 mmol, 1.0 equiv.), enamine ester 32
(
2
53.6 mg, 0.316 mmol, 2.0 equiv.), MgBr (70.0 mg, 0.380 mmol, 2.4 equiv.), and 4 Å
mol. Sieves (100 mg) in toluene (1.7 mL). The second step was performed in the same
pot by the addition of Pd/C (69.5 mg, 5 wt. %). Purification by flash chromatography (20-
4
0% EtOAC / hexanes) gave product 34 (31.5 mg, 0.081 mmol, 51%) as colorless oil.
-
1
1
IR: (neat) 2940, 2894, 1699, 1576, 1473, 1428, 1268, 1202, 1080, 998 cm ; H NMR
400 MHz; CDCl ): δ 8.45 (d, J = 2.3 Hz, 1H), 7.87 (d, J = 2.3 Hz, 1H), 7.44-7.47 (m,
H), 7.36-7.42 (m, 5H), 7.28-7.30 (m, 2H), 4.18 (q, J = 7.1 Hz, 2H), 4.10 (t, J = 7.2 Hz,
(
3
2
1
1
1
1
3
3
H), 3.22-3.32 (m, 2H), 1.12 (t, J = 7.1 Hz, 3H) ppm; C NMR (100 MHz, CDCl ) δ
67.5, 157.0, 152.0, 138.9, 138.2, 135.1, 134.1, 130.2, 130.1, 129.5, 128.9, 128.4,
27.6, 127.3, 126.9, 119.6, 61.9, 39.1, 38.7, 13.9 ppm; HRMS (ESI+) calcd. for
C
23
H
20
N
2
O
2
Cl (M+H) 391.1208, found 391.1200.
S25

References:
1
2
3
4
5
2
6
7
8
1
9
1
1
1
1
1
1
1
1
. B. M. Trost, J. R. Miller, C. M. Hoffman, Jr., J. Am. Chem. Soc. 2011, 133, 8165-8167.
. X. Wang, M. Kitamura, K. Maruoka, J. Am. Chem. Soc. 2007, 129, 1038-1039.
. M. Dʼhooghe, A. Waterinckx, N. De Kimpe, J. Org. Chem. 2005, 70, 227-232.
. D. J. St. Cyr, B. A. Arndtsen, J. Am. Chem. Soc. 2007, 129, 12366-12367.
. K. A. Tehrani, V. T. Nguyen, M. Karikomi, M. Rottiers, N. De Kimpe, Tetrahedron
002, 58, 7145-7152.
. K. Afarinkia, C. W. Rees, J. I. G. Cadogan, Tetrahedron 1990, 46, 7175-7196.
. K. Okuro, J. Gurnham, H. Alper, Tetrahedron Lett. 2012, 63, 620-622.
. A. R. Ickes, S. C. Ensign, A. K. Gupta, K. L. Hull, J. Am. Chem. Soc. 2014, 136,
1256-11259.
. E. J. Corey, C. P. Decicco, R. C. Newbold, Tetrahedron Lett. 1991, 32, 5287-5290.
0. J.-M. Huang, J.-F. Zhang, Y. Dong, W. Gong, J. Org. Chem. 2011, 76, 3511-3514.
1. R. A. G. Smith, J. R. Knowles, J. Chem. Soc., Perkin Trans. 2 1975, 686-694.
2. E. J. Roskamp, P. S. Dragovich, J. B. Hartung, Jr., S. F. Pedersen, J. Org. Chem.
989, 54, 4736-4737.
3. M. S. Sigman, P. Vachal, E. N. Jacobsen, Angew. Chem. Int. Ed. 2000, 39, 1279-
281.
4. A. Lumbroso, N. Abermil, B. Briet, Chem. Sci. 2012, 3, 789-793.
5. C. B. Kanner, U. K. Pandit, Tetrahedron 1982, 38, 3597-3564.
S26

7.260
3.465
3.446
3.428
3.409
1.544
1.525
1.489
S27

165.604
117.895
84.039
77.478
77.160
76.842
3
2.629
7.866
2
15.363
S28

7.260
3.399
3.381
3.364
1.922
1.903
1.884
1.865
1.491
1.477
1.466
1.456
1.446
1.437
1.369
1.352
1.332
1.326
1.319
1.310
1.301
1.293
0.897
0.881
0.864
S29

165.370
117.148
83.961
77.478
77.160
76.842
38.752
31.506
30.021
28.610
27.919
26.797
22.591
14.122
S30