Versatile CuI/Pd0 dual catalysis for the synthesis of quaternary α-allylated carbonyl compounds: Development, mechanistic investigations and scope

Article abstract of DOI:10.1002/chem.201404015

We report herein a versatile cooperative dual catalysis reaction based on a Cu^I/Pd⁰ system. Mechanistic investigation shows that every component plays a crucial role in determining the reaction outcome. The reaction is successfully extended to various substrates; such as α,β-unsaturated ketones, malonates and coumarins. The strategy tolerates different substitution patterns and affords good yields for each family of substrates.

Full text of DOI:10.1002/chem.201404015

Supporting Information
ꢀ
Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2014
I
0
Versatile Cu /Pd Dual Catalysis for the Synthesis of Quaternary
a-Allylated Carbonyl Compounds: Development, Mechanistic
Investigations and Scope
[
a]
Fady Nahra, Yohan Macꢀ, Arnaud Boreux, Francois Billard, and Olivier Riant*
chem_201404015_sm_miscellaneous_information.pdf

Supporting information
Table of contents
I. Instrumentation and Chemicals............................................................................................... 2
II. α,β-unsaturated ketones:........................................................................................................ 3
II.1. General procedure for the sequential 1,4 reduction/AAA reaction............................ 3
II.2. Preparation of the starting materials 4a-k................................................................... 4
II.3. General procedure for the dual catalysis reaction..................................................... 10
II.4. Sequential and mechanistic tests .............................................................................. 15
III. α,β-unsaturated malonates:................................................................................................. 19
III.1. Preparation of the starting materials 8a-j ................................................................ 19
III.2. General procedure for the dual catalysis reaction ................................................... 24
IV. Coumarines: ....................................................................................................................... 28
IV.1. Preparation of the starting materials 11a-b ............................................................. 28
IV.2. General Procedure for the dual catalysis reaction................................................... 29
IV.3. General procedure for the multicatalysis: Selective formation of product 14 and 14’
.
......................................................................................................................................... 30
IV.4. General procedure for the ring-closing metathesis ................................................. 31
V. Spectras ....................................................................................................................... 33
S-1

I. Instrumentation and Chemicals
Unless otherwise noted, all manipulations were performed under an argon atmosphere
using standard Schlenk-type glassware. Toluene was distilled on sodium under an argon
1
atmosphere then degassed. Diethyl ether and THF were distilled on sodium/benzophenone
under an argon atmosphere. Dichloromethane was distilled on CaH . Solvents used for work-
2
up were of technical grade. Commercial reagents were purchased from Acros, Sigma-Adrich,
1
13
ABCR, TCI or Apollo scientific and used as received unless stated otherwise. H and C
1
13
NMR spectra were recorded on Bruker-300 and Bruker-500 spectrometers. H and C NMR
chemical shifts are reported relative to CDCl (7.26, 77.16 ppm). Multiplicity is given as
3
follows: s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet and br = broad. High
resolution Mass Spectra were obtained from a Thermo Scientific QExactive, with accurate
+
mass reported for the molecular ion [M+H] or suitable fragment ions. GC analyses were
recorded on a ThermoFinningan Trace GC apparatus with a CHIRALSIL-DEX CB (25m,
0
4
.25 mm, 25 µm) column. Column chromatography was carried out on silica gel (ROCC 60,
0-63 µm). TLC analyses were performed on commercial aluminum plates bearing a 0.25 mm
2
3
layer of Merck Silica gel 60F . IMesCuCl and IMesCuDBM were prepared by literature
254
methods.
1
Preparation of the toluene distillation is crucial to obtain reproducible results. It should be carried out as
follows: Toluene should be distilled in a 1 L distillation flask on 6 g of sodium, then degassed for 1 hr under
argon before use. It could be stored and used for no more than one week.
2
a) Cazin. S. J., Dalton Trans. 2010, 39, 4489–4491, b) Nolan S. P., Organometallics 2004, 23, 1157-1160 , c)
Nolan S. P., J. of Organometallic Chem. 2000, 606, 49 – 54.
3
A. Welle, S. Diez-Gonzalez, B. Tinant, S. P. Nolan, O. Riant Org. Lett. 2006, 8, 6059-6062.
S-2

II. α,β-unsaturated ketones:
II.1. General procedure for the sequential 1,4 reduction/AAA reaction
OBoc
(
IMes)Cu(DBM)(2 mol%)
Pd(OAc) (7 mol%)
dppe(10 mol%)
TBAT(35 mol%)
SiR3
2
O
O
O
t-BuOK(2 mol%)
Me(EtO) SiH (1.1 eq.)
2
o
o
Toluene, 0 C, 1h
Toluene, 45 C
2
4h
1, 90%
d.r. = 75/25
D-(+)-Carvone
In Situ
General procedure for the preparation of the silyl enolate (in situ):
A flame-dried Schlenk was charged sequentially with the copper catalyst (10.2 mg, 0.02
mmol, 0.02 eq.), t-BuOK (2.4 mg, 0.02 mmol, 0.02 eq.) and 1 mL of the designated solvent
o
(
THF or toluene). Carvone was then added (153.3 mg, 1 mmol, 1 eq.) at 0 C, followed by the
silane (1.7 mmol, 1.7 eq.). The reaction was monitored by TLC and after total consumption of
the starting materiel (1hour), the reaction mixture was used in the next step without any
further purification.
General procedure for the sequential reaction:
A flame-dried Schlenk was charged sequentially with the indicated amount of the
palladium complex, dppe (0.1 mmol, 0.1 eq.) and 0.5 mL of the indicated solvent. The
reaction mixture was stirred at room temperature. After 5 minutes the tert-butyl allylcarbonate
(1.5 mmol, 1.5 eq.) was added, followed by the additive (if indicated) and the mixture was
stirred for an additional 5 minutes. The silyl enolate solution obtained above was then
transferred to the palladium solution at the indicated temperature. After 24 hours, 1.4 mL of
TBAF (1M in THF) was added to the reaction mixture followed by a saturated aqueous
solution of NH Cl and Et O. The two phases were then separated and the aqueous layer was
4
2
extracted three times with Et O. The combined organic layers were dried over MgSO and
2
4
concentrated in vacuo. The residue was purified by column chromatography (petroleum ether/
Et O, 96/4) to give the two diastereoisomers of the desired product.
2

(5S)-2-allyl-2-methyl-5-(prop-1-en-2-yl)cyclohexanone (1)
S-3

1
Diastereoisomer 1a (Major): H NMR (300 MHz, CDCl ) δ = 5.70 – 5.53
3
O
(m, 1H), 5.10 – 4.98 (m, 2H), 4.79 – 4.64 (m, 2H), 2.53 – 2.27 (m, 4H),
2
.21 – 2.14 (m, 1H), 1.93 – 1.83 (m, 1H), 1.82 – 1.65 (m, 5H), 1.56 – 1.42
1
3
(
m, 1H), 1.02 (s, 3H). C NMR (75 MHz, CDCl3) δ = 214.76, 147.60,
1
33.01, 118.31, 109.97, 48.13, 46.24, 43.62, 41.57, 37.59, 26.11, 22.27, 20.80. HRMS m/z
+
calcd. for C H O [M + H] 193.15869; found 193.15885.
1
3
21
1
1
Diastereoisomer 1b (Minor): H NMR (300 MHz, CDCl ) δ = 5.87 – 5.63 (m, 1H), 5.04 (dd,
3
J = 13.7, 4.1 Hz, 2H), 4.83 – 4.63 (m, 2H), 2.59 – 2.16 (m, 4H), 1.88 – 1.56 (m, 6H), 1.30 –
1
3
1
1
.18 (m, 2H), 1.13 (s, 3H). C NMR (75 MHz, CDCl ) δ = 215.04, 147.67, 134.77, 117.95,
3
10.06, 47.41, 45.95, 43.50, 42.52, 36.40, 26.25, 23.21, 20.83. HRMS m/z calcd. for
+
C H O [M + H] 193.15869; found 193.15881.
13
21
1
II.2. Preparation of the starting materials 4a-k
O
O
O
1
) Pd(PPh ) Cl
DMF, 0 C -> r.t.
3
o
2
2
I2, Pyridine
I
R
CH Cl2
n = 0, 1
2
n
n
RZnBr
n
2-iodoenones
4a-h
4
Preparation of α-iodoenones :
In a 500 mL round-bottomed three necked flask immersed in a water bath and equipped with
an addition funnel were placed the cyclic enone (25.5 mmol, 1 eq.) and 1/5 pyridine-CH Cl
2
2
(
43 mL). To this was added dropwise a solution of I (7.8 g, 31 mmol, 1.2 eq.) in 43 mL of
2
1
5
/5 pyridine-CH Cl over 1 hour. The mixture was stirred for an additional 4h, quenched with
2 2
0 mL of citric acid (6% aqueous solution), and extracted 3 times with CH Cl . The combined
2
2
organic layers were washed with an aqueous 10% solution of Na S O , 1M HCl and brine,
2
2
3
dried over MgSO , and concentrated in vacuo. The crude product was purified by column
4
chromatography (silica gel, petroleum ether/EtOAc, 29/1) to afford the desired product.

2-iodocyclohex-2-enone
O
Prepared according to the general procedure described above. The crude product
was purified by column chromatography (silica gel, petroleum ether/EtOAc :
I
4
E. Negishi, Z. Tan, S.-Y. Liou, B. Liao Tetrahedron 2000, 56, 10197-10207.
S-4

1
2
7
6
9/1) to afford the desired product in 87% yield (4.95 g). H NMR (300 MHz, CDCl ) δ =
3
.77 (t, J = 4.4 Hz, 1H), 2.72 – 2.59 (m, 2H), 2.44 (td, J = 6.0, 4.6 Hz, 2H), 2.09 (dt, J = 12.2,
1
3
.1 Hz, 2H). C NMR (75 MHz, CDCl ) δ = 192.35, 159.56, 104.02, 37.39, 30.07, 22.98.
3
4
Spectral data are identical to those reported in the literature.

2-iodocyclopent-2-enone
Prepared according to the general procedure described above. The crude product
O
I
was purified by column chromatography (silica gel, petroleum ether/EtOAc :
1
2
9/1) to afford the desired product in 61% yield (3.33 g). H NMR (300 MHz,
1
3
CDCl ) δ = 8.01 (t, J = 2.9 Hz, 1H), 2.84 – 2.69 (m, 2H), 2.60 – 2.37 (m, 2H). C NMR (75
3
MHz, CDCl ) δ = 204.11, 169.76, 102.98, 31.25, 30.84.
3
4
Spectral data are identical to those reported in the literature.
5
General procedure for the preparation of 4a,e :
A flame dried Schlenk was charged with ZnBr (1.3 eq.) which was then flame dried and
2
flushed with Ar. To this were added THF (1.1 mL per mmol of ZnBr ) and n-BuLi (1.3 eq.,
2
o
2
.5 M in hexane) or n-PrMgBr (1.3 eq., 1 M in THF) at -78 C. The mixture was allowed to
o
reach 0 C. Then was canulated into a solution of α-iodoenone (1 eq.), Pd(PPh ) Cl (0.05
3
2
2
o
equiv. to enone) in DMF (3.7 mL per mmol of enone) at 0 C. The reaction mixture was
stirred for 3 h at room temperature, quenched with aqueous NH Cl and c.c. NH OH, and
4
4
extracted 3 times with Et O. The organic layers were washed with water, 1M HCl, 5% aq.
2
NaHCO , 10% aq. LiCl (2 times) and brine, dried over MgSO , and concentrated. Fractional
3
4
distillation afforded the desired product.

2-butylcyclohex-2-enone (4a)
Prepared according to the general procedure described above to afford the
O
n-Bu
1
desired product in 44% yield. H NMR (300 MHz, CDCl ) δ = 6.69 (t, J = 4.2
3
Hz, 1H), 2.46 – 2.38 (m, 2H), 2.38 – 2.29 (m, 2H), 2.22 – 2.12 (m, 2H), 1.97
1
3
(
dt, J = 12.3, 6.1 Hz, 2H), 1.44 – 1.21 (m, 4H), 0.89 (t, J = 7.0 Hz, 3H). C NMR (75 MHz,
CDCl ) δ = 199.78, 144.94, 140.12, 38.78, 30.92, 29.37, 26.21, 23.33, 22.64, 14.09.
3
S-5

4
Spectral data are identical to those reported in the literature.

2-butylcyclopent-2-enone (4e)
Prepared according to the general procedure described above to afford the
O
1
n-Bu
desired product in 50% yield. H NMR (300 MHz, CDCl ) δ = 7.33 – 7.27 (m,
3
1
H), 2.60 – 2.49 (m, 2H), 2.44 – 2.34 (m, 2H), 2.22 – 2.08 (m, 2H), 1.53 – 1.40
1
3
(
m, 2H), 1.40 – 1.23 (m, 2H), 0.91 (t, J = 7.2 Hz, 3H). C NMR (75 MHz, CDCl ) δ =
3
2
10.15, 157.35, 146.59, 34.69, 29.98, 26.51, 24.56, 22.56, 13.92.
4
Spectral data are identical to those reported in the literature
4
General procedure for the preparation of 4c :
A flame-dried round-bottomed three necked flask, equipped with a reflux condenser, was
charged with Mg turnings (1.7 eq.) and a catalytic amount of iodine in THF (0.7 mL per
mmol of Mg). The mixture was refluxed for 30 minutes under argon. The mixture was then
o
allowed to cool down to 65 C, and the alkyl bromide (1.3 eq) was added at that temperature
over 20 minutes. At the end of the addition, the mixture was again refluxed for 1 hour.
Afterwards, the mixture was cooled to room temperature. The supernatant was collected and
used as the Grignard reagent later on in the procedure.
A flame-dried Schlenk was charged with ZnBr (0.65 eq.) which was then flame-dried and
2
flushed with Ar. To this were added THF (1 mL per mmol of ZnBr ) and the above prepared
2
o
o
Grignard reagent (1.3 eq.) at -78 C. The mixture was allowed to reach 0 C (R Zn is formed
2
in this procedure). Then was cannulated into a solution of α-iodoenone (1 eq.), Pd(PPh ) Cl
2
3
2
o
(
0.05 equiv. to enone) in DMF (3.7 mL per mmol of enone) at 0 C. The reaction mixture was
stirred for 3 h at room temperature, quenched with aqueous NH Cl and c.c. NH OH, and
4
4
extracted 3 times with Et O. The organic layers were washed with water, 1M HCl, 5% aq.
2
NaHCO , 10% aq. LiCl (2 times) and brine, dried over MgSO , and concentrated. Fractional
3
4
distillation afforded the desired product.

2-propylcyclohex-2-enone (4c)
S-6

Prepared according to the general procedure described above, using 1-
O
n-Pr
1
bromopropane, to afford the desired product in 35% yield. H NMR (300 MHz,
CDCl ) δ = 6.70 (t, J = 4.2 Hz, 1H), 2.50 – 2.30 (m, 4H), 2.15 (td, J = 7.7, 1.3
3
13
Hz, 2H), 1.97 (dt, J = 12.3, 6.2 Hz, 2H), 1.48 – 1.33 (m, 2H), 0.89 (t, J = 7.4 Hz, 3H). C
NMR (75 MHz, CDCl ) δ = 199.84, 145.13, 139.81, 38.77, 31.74, 26.21, 23.34, 21.87, 14.01.
3
5
Spectral data are identical to those reported in the literature.
4
General procedure for the preparation of 4b,d,f,g :
A fame dried three-necked flask equipped with a septum inlet, magnetic stirring bar and a
condenser was charged with Zn dust (2.0 eq.) and then flushed with Ar. To this were added
THF (0.5 mL per mmol of Zn) and and 1,2-dibromoethane (0.03 eq. to Zn). This suspension
was heated to reflux for 20 min and then cooled to room temperature. A solution of I (0.0025
2
eq. to Zn) in THF (1 ml per 0.1 mmol of I ) and 1,2-dibromoethane (0.01 eq. to Zn) were
2
o
added. This suspension was again heated to reflux for 20 min and then cooled to 0 C. Benzyl
bromide (1.0 eq) was added dropwise, and the mixture was stirred at room temperature for 3
h. The mixture was then canulated into a solution of α-iodoenone (0.8 eq.), Pd(PPh ) Cl
2
3
2
o
(
0.05 equiv. to enone) in DMF (3.7 mL per mmol of enone) at 0 C. The reaction mixture was
o
stirred for 3 h at room temperature then overnight at 50 C, quenched with aqueous NH Cl
4
and c.c. NH OH, and extracted 3 times with Et O. The organic layers were washed with
4
2
water, 1M HCl, 5% aq. NaHCO , 10% aq. LiCl (2 times) and brine, dried over MgSO , and
3
4
concentrated. Flash chromatography (silica gel, petroleum ether/EtOAc : 29/1) provided the
desired product.

2-benzylcyclohex-2-enone (4b)
Prepared according to the general procedure described above to afford the
O
1
desired product in 66% yield. H NMR(300 MHz, CDCl ) δ = 7.33 – 7.24 (m,
Ph
3
2
H), 7.23 – 7.13 (m, 3H), 6.56 (t, J = 4.1 Hz, 1H), 3.52 (s, 2H), 2.51 – 2.40 (m,
1
3
2
1
H), 2.38 – 2.27 (m, 2H), 2.06 – 1.91 (m, 2H). C NMR (75 MHz, CDCl ) δ = 199.16,
3
46.54, 139.80, 139.65, 129.32, 128.49, 126.19, 38.62, 35.55, 26.22, 23.18.
4
Spectral data are identical to those reported in the literature.
S-7


2-(3-methoxybenzyl)cyclohex-2-enone (4d)
1
Prepared according to the general procedure described above. H NMR
300 MHz, CDCl ) δ = 7.20 (t, J = 7.8 Hz, 1H), 6.80 – 6.68 (m, 3H),
O
OMe
(
3
6
.57 (t, J = 4.2 Hz, 1H), 3.79 (s, 3H), 3.49 (s, 2H), 2.52 – 2.39 (m, 2H),
1
3
2
1
.39 – 2.25 (m, 2H), 2.07 – 1.89 (m, 2H). C NMR (75 MHz, CDCl ) δ = 199.14, 159.74,
3
46.65, 141.42, 139.43, 129.44, 121.73, 115.08, 111.46, 55.30, 38.62, 35.55, 26.23, 23.18.
+
HRMS m/z calcd. for C H O [M + H] 217.12231; found 217.12245.
1
4
17
2

2-benzylcyclopent-2-enone (4f)
Prepared according to the general procedure described above to afford the
O
1
desired product in 30% yield. H NMR (300 MHz, CDCl ) δ = 7.34 – 7.25 (m,
3
Ph
2
H), 7.25 – 7.17 (m, 3H), 7.17 – 7.11 (m, 1H), 3.49 (br. s, 2H), 2.54 (td, J =
1
3
4
1
.6, 2.2 Hz, 2H), 2.49 – 2.37 (m, 2H). C NMR (75 MHz, CDCl ) δ = 209.26, 158.91,
3
46.18, 139.01, 129.04, 128.63, 126.40, 34.73, 31.47, 26.60.
4
Spectral data are identical to those reported in the literature.

2-phenethylcyclohex-2-enone (4g)
Prepared according to the general procedure described above to afford
O
1
the desired product in 65% yield. H NMR (300 MHz, CDCl ) δ = 7.18
3
F
– 7.04 (m, 2H), 7.03 – 6.88 (m, 2H), 6.57 (t, J = 4.2 Hz, 1H), 3.48 (s,
13
2
H), 2.53 – 2.40 (m, 2H), 2.40 – 2.27 (m, 2H), 2.12 – 1.88 (m, 2H). C NMR (75 MHz,
CDCl ) δ = 198.93, 146.41, 139.42, 135.29, 130.53, 130.42, 115.24, 114.96, 38.46, 34.77,
3
1
9
2
6.08, 23.02. F NMR (282 MHz, CDCl ) δ = -117.42. HRMS m/z calcd. for C H F O [M
3 13 14 1 1
+
+
H] 205.10232; found 205.10252.
6
General procedure for the preparation of 4h,i,j,k :
5
G. Chelucci, S. Gladiali, J. Heterocyclic Chem. 1986, 23, 1761-1765.
6
F.-X. Felpin, J. Org. Chem. 2005, 70, 8575-8578.
S-8

To a solution of α-iodoenone (1.5 mmol, 1 eq.) in DME (4.5 mL) and H O (4.5 mL) were
2
added Na CO (318 mg, 3 mmol, 2 eq.), Ar-B(OH) (3 mmol, 2 eq.), and 10% Pd/C (79.5 mg,
2
3
2
o
5
mol% of Pd). The mixture was stirred for 80 C for 5 hours. Pd/C was filtered, and the
filtrate was diluted with H O (4.5 mL) and extracted with Et O (3 times). The collected
2
2
organic extracts were dried on MgSO and concentrated under reduced pressure. Flash
4
chromatography (silica gel, petroleum ether/EtOAc, 29/1) provided the desired product.

2-phenylcyclohex-2-enone (4h)
Prepared according to the general procedure described above to afford the
O
Ph
1
desired product in 60% yield. H NMR (300 MHz, CDCl ) δ = 7.42 – 7.23 (m,
3
1
3
5
H), 7.03 (t, J = 4.3 Hz, 1H), 2.67 – 2.46 (m, 4H), 2.22 – 2.00 (m, 2H). C
NMR (75 MHz, CDCl ) δ = 198.06, 148.07, 140.57, 136.70, 128.76, 128.13, 127.69, 39.22,
3
2
6.76, 23.08.
6
Spectral data are identical to those reported in the literature.

2-p-tolylcyclohex-2-enone (4i)
Prepared according to the general procedure described above to afford the
O
1
desired product in 71% yield. H NMR (300 MHz, CDCl ) δ = 7.24 – 7.11
3
(m, 4H), 7.00 (t, J = 4.3 Hz, 1H), 2.67 – 2.47 (m, 4H), 2.35 (s, 3H), 2.17 –
1
3
2
1
1
.05 (m, 2H). C NMR (75 MHz, CDCl ) δ = 198.10, 147.32, 140.33, 137.32, 133.68,
3
+
28.73, 128.50, 39.11, 26.61, 22.99, 21.17. HRMS m/z calcd. for C H O [M + H]
1
3
15
1
87.11199; found 187.11174.

2-(4-fluorophenyl)cyclohex-2-enone (4j)
Prepared according to the general procedure described above to afford the
F
O
1
desired product in 68% yield. H NMR (300 MHz, CDCl ) δ = 7.42 – 7.16
3
(m, 2H), 7.14 – 6.95 (m, 3H), 2.70 – 2.47 (m, 4H), 2.17 – 2.04 (m, 2H).
1
3
C NMR (75 MHz, CDCl ) δ = 197.93, 147.95, 139.45, 132.48, 130.35, 130.24, 115.02,
3
19
1
14.74, 39.00, 26.60, 22.90. F NMR (282 MHz, CDCl ) δ = -114.89. HRMS m/z calcd. for
3
+
C H F O [M + H] 191.08681; found 191.08667.
12
12
1
1

2-phenylcyclopent-2-enone (4k)
S-9

Prepared according to the general procedure described above to afford the
O
1
Ph
desired product in 68% yield. H NMR (300 MHz, CDCl ) δ = 7.83 (t, J = 2.9
3
Hz, 1H), 7.68 (dt, J = 3.7, 2.1 Hz, 2H), 7.50 – 7.28 (m, 3H), 2.79 – 2.66 (m, 2H),
1
3
2
1
.66 – 2.51 (m, 2H). C NMR (75 MHz, CDCl ) δ = 207.58, 158.92, 143.50, 131.68, 128.42,
3
28.35, 127.05, 35.80, 26.22.
6
Spectral data are identical to those reported in the literature.
II.3. General procedure for the dual catalysis reaction
General procedure for the diastereoselective dual catalysis reaction (optimised conditions
for 1):
(
IMes)CuDBM (5 mol%)
O
O
Pd(OAc) / (S)-Ph-PHOX (1/2.5 mol%)
Me(EtO) SiH (1.7 eq)
*
+
OCO Me
THF, r.t., 24h
D-(+)-Carvone
1
, 82% (75%)
d.r. = 95/5
A flame-dried Schlenk was charged sequentially with the palladium acetate (2.3 mg, 0.01
mmol, 0.01 eq.), (S)-Ph-PHOX (10.2 mg, 0.025 mmol, 0.025 eq.) and 0.5 mL of toluene. The
reaction mixture was stirred at room temperature. After 5 min the allylcarbonate (0.18 mL,
1
.5 mmol, 1.5 eq.) was added and the mixture was stirred for an additional 5 min.
Simultaneously another flame-dried Schlenk was charged with IMesCuDBM (30 mg, 0.05
mmol, 0.05 eq.) in 0.5 mL of toluene. Once the palladium acetate was totally dissolved, the
palladium mixture was transferred into the Schlenk containing the copper catalyst followed
immediately by the Carvone (153.3 mg, 1 mmol, 1 eq.). The silane (0.28 mL, 1.7 mmol, 1.7
eq.) was diluted in 0.5 mL of toluene and quickly added. After 24 hours, 1.4 mL of TBAF
(1M in THF) was added to the reaction mixture. The latter was then filtered on a plug silica
gel (eluting with petroleum ether/ Et O : 4/1). The filtrate was concentrated in vacuo to obtain
2
a colorless residue. The residue was purified by column chromatography (petroleum ether/
Et O, 96/4) to give the desired product 1 (145 mg, 75%, d.r. = 95/5).
2
S-10

General procedure for the enantioselective dual catalysis reaction (optimised conditions for
a-h):
4
A flame-dried Schlenk was charged sequentially with the palladium acetate (1.2 mg, 0.005
mmol, 0.01 eq.), (S)-tBu-PHOX (10.2 mg, 0.0125 mmol, 0.025 eq.) and 0.4 mL of toluene.
The reaction mixture was stirred at room temperature. After 5 min the allylcarbonate (0.12
mL, 1 mmol, 2.0 eq.) was added and the mixture was stirred for an additional 5 minutes.
Simultaneously another flame-dried Schlenk was charged with IMesCuCl (10.1 mg, 0.025
mmol, 0.05 eq.) and KOtBu (5.8 mg, 0.05 mmol, 0.1 eq.) in 0.4 mL of toluene and stirred for
1
min. Once the palladium acetate was totally dissolved, the palladium mixture was
transferred into the Schlenk containing the copper catalyst followed immediately by the
Michael acceptor 4a-h (0.5 mmol, diluted in 0.2 mL of toluene). The mixture was then
o
immediately heated to 45 C and the silane (0.14 mL, 0.85 mmol, 1.7 eq.) was quickly added
(without dilution). After 24 hours, 0.7 mL of TBAF (1M in THF) was added to the reaction
mixture. The latter was then filtered on a plug silica gel (eluting with petroleum ether/ Et O :
2
4
/1). The filtrate was concentrated in vacuo to obtain a colorless residue. A sample of this
residue was taken for GC and NMR analysis. The residue was purified by column
chromatography (petroleum ether/ Et O) to give the desired product 5a-h.
2

2-allyl-2-butylcyclohexanone (5a)
1
Prepared according to the general procedure described above. H NMR (300
O
n-Bu
MHz, CDCl ) δ = 5.68 (ddt, J=15.1, 11.4, 7.4 Hz, 1H), 5.10 – 4.91 (m, 2H),
3
2
.49 – 2.13 (m, 4H), 1.97 – 1.80 (m, 1H), 1.81 – 1.56 (m, 6H), 1.48 – 1.34 (m,
1
3
1
H), 1.32 – 1.16 (m, 3H), 1.04 – 0.92 (m, 1H), 0.88 (t, J=7.1 Hz, 3H). C NMR (75 MHz,
CDCl ) δ = 215.26, 134.43, 117.77, 51.56, 39.39, 39.18, 36.68, 34.62, 27.34, 25.67, 23.45,
3
S-11

+
2
0.95, 14.13. HRMS m/z calcd. for C H O [M + H] 195.17434; found 195.17446. The
13 23 1
enantiomeric ratio was determined by chiral GC (T = 118 °C (27 min), t = 20.4 min (6.38
R
%
), t = 20.8 min (93.62 %)).
R

2-allyl-2-benzylcyclohexanone (5b)
1
Prepared according to the general procedure described above. H NMR (300
O
MHz, CDCl ) δ = 7.32 – 7.17 (m, 3H), 7.16 – 7.08 (m, 2H), 5.74 (ddt, J=17.4,
Ph
3
1
0.3, 7.2, 1H), 5.08 (m, 2H), 2.91 (s, 2H), 2.53 – 2.37 (m, 2H), 2.29 (d, J=7.2
1
3
Hz, 2H), 1.77 (m, 6H). C NMR (75 MHz, CDCl ) δ = 214.25, 137.69, 133.89, 130.72,
3
1
28.08, 126.42, 118.31, 52.69, 40.96, 39.72, 39.35, 35.65, 26.89, 20.93. HRMS m/z calcd. for
+
C H O [M + H] 229.15869; found 229.15882. The enantiomeric ratio was determined by
16
21
1
o
chiral GC (T = 110-170 °C (1 C/min), t = 52 min (91.8 %), t = 52.4 min (8.2 %)).
R
R

2-allyl-2-propylcyclohexanone (5c)
1
Prepared according to the general procedure described above. H NMR (300
O
n-Pr
MHz, CDCl ) δ = 5.80 – 5.57 (m, 1H), 5.12 – 4.90 (m, 2H), 2.47 – 2.17 (m,
3
4
H), 1.93 – 1.83 (m, 1H), 1.74 – 1.58 (m, 5H), 1.46 – 1.23 (m, 4H), 0.88 (t,
1
3
J=7.1 Hz, 3H). C NMR (75 MHz, CDCl ) δ = 215.13, 134.42, 117.75, 51.70, 39.38, 39.27,
3
+
3
1
7.32, 36.66, 27.34, 20.96, 16.82, 14.86. HRMS m/z calcd. for C H O [M + H]
12 21 1
81.15869; found 181.15895. The enantiomeric ratio was determined by chiral GC (T = 115
°
C (30 min), t = 16.1 min (7.1 %), t = 16.5 min (92.9 %)).
R R

2-allyl-2-(3-methoxybenzyl)cyclohexanone (5d)
1
Prepared according to the general procedure described above. H NMR
300 MHz, CDCl ) δ = 7.16 (t, J=7.8 Hz, 1H), 6.80 – 6.63 (m, 3H),
O
OMe
(
3
5
.73 (ddt, J=17.5, 10.4, 7.2 Hz, 1H), 5.16 – 5.00 (m, 2H), 3.77 (s, 3H),
1
3
2
.88 (s, 2H), 2.53 – 2.38 (m, 2H), 2.30 (d, J=7.2 Hz, 2H), 1.90 – 1.61 (m, 6H). C NMR (75
MHz, CDCl ) δ = 214.19, 159.33, 139.32, 133.89, 128.96, 123.19, 118.31, 116.72, 111.56,
3
5
5.22, 52.68, 40.97, 39.70, 39.43, 35.74, 26.90, 20.95. HRMS m/z calcd. for C H O [M +
17 23 2
+
H] 259.16926; found 259.16940. The enantiomeric ratio was determined by chiral GC (T =
o
1
50 °C (40 min) to 170 °C (1 C/min), t = 60.3 min (86.2 %), t = 60.6 min (13.8 %)).
R
R
S-12


2-allyl-2-butylcyclopentanone (5e)
1
Prepared according to the general procedure described above. H NMR (500
O
n-Bu
MHz, CDCl ) δ = 5.68 (ddt, J=16.6, 10.5, 7.4 Hz, 1H), 5.09 – 4.99 (m, 2H),
3
2
.25 – 2.09 (m, 4H), 1.96 – 1.77 (m, 4H), 1.42 – 1.36 (m, 2H), 1.34 – 1.19 (m,
1
3
4
3
H), 0.87 (t, J=7.2 Hz, 3H). C NMR (126 MHz, CDCl ) δ = 223.1, 134.21, 118.18, 51.81,
3
9.96, 38.63, 35.29, 32.82, 26.43, 23.45, 18.90, 14.13. HRMS m/z calcd. for C H O [M +
1
2
21
1
+
H] 181.15869; found 181.15901. The enantiomeric ratio was determined by chiral GC (T =
o
1
00-140°C (1 C/min), t = 19.6 min (10.5 %), t = 19.9 min (89.5 %)).
R
R

2-allyl-2-benzylcyclopentanone (5f)
1
Prepared according to the general procedure described above. H NMR (300
O
MHz, CDCl ) δ = 7.29 – 7.19 (m, 3H), 7.15 – 7.00 (m, 2H), 5.83 – 5.61 (m,
3
Ph
1
H), 5.21 – 4.93 (m, 2H), 2.92 (d, J=13.3 Hz, 1H), 2.60 (d, J=13.3 Hz, 1H),
2
1
1
+
.36 – 2.22 (m, 1H), 2.22 – 2.08 (m, 2H), 2.03 – 1.80 (m, 3H), 1.83 – 1.66 (m, 1H), 1.54 –
1
3
.40 (m, 1H). C NMR (75 MHz, CDCl ) δ = 223.00, 137.92, 133.81, 130.42, 128.33,
3
26.59, 118.82, 53.36, 41.89, 41.08, 39.02, 31.18, 18.80. HRMS m/z calcd. for C H O [M
1
5
19
1
+
H] 215.14304; found 215.14324. The enantiomeric ratio was determined by chiral GC (T =
o
o
1
21 C (60 min) to 160 °C (1 C/min), t = 71.1 min (87.4 %), t = 71.6 min (12.6 %)).
R
R

2-allyl-2-(4-fluorobenzyl)cyclohexanone (5g)
1
Prepared according to the general procedure described above. H NMR
300 MHz, CDCl ) δ = 7.16 – 7.01 (m, 2H), 7.01 – 6.85 (m, 2H), 5.70
O
(
3
F
(ddt, J=17.3, 10.3, 7.2, 1H), 5.21 – 4.96 (m, 2H), 2.91 (d, J=13.9, 1H),
1
3
2
.82 (d, J=13.9, 1H), 2.50 – 2.37 (m, 2H), 2.33 – 2.20 (m, 2H), 1.92 – 1.56 (m, 6H). C NMR
(
75 MHz, CDCl ) δ = 214.01, 163.36, 160.12, 133.63, 132.17, 132.07, 118.48, 115.02,
3
1
9
1
1
14.74, 52.70, 40.15, 39.70, 39.53, 35.55, 26.83, 20.92. F NMR (282 MHz, CDCl ) δ = -
3
+
16.95. HRMS m/z calcd. for C H O F [M + H] 247.14927; found 247.14935. The
1
6
20
1 1
o
enantiomeric ratio was determined by chiral GC (T 110-170 °C (1 C/min), t = 53.8 min
R
(
71.6 %), t = 54.4 min (28.4 %)).
R

2-allyl-2-phenylcyclohexanone (5h)
S-13

1
Prepared according to the general procedure described above. H NMR (300
O
Ph
MHz, CDCl ) δ = 7.39 – 7.28 (m, 2H), 7.28 – 7.19 (m, 1H), 7.18 – 7.10 (m,
3
2
H), 5.44 (dddd, J=17.0, 10.3, 7.8, 6.9 Hz, 1H), 5.00 – 4.78 (m, 2H), 2.72 –
2
4
5
2
.60 (m, 1H), 2.57 – 2.39 (m, 2H), 2.36 – 2.21 (m, 2H), 2.00 – 1.87 (m, 1H), 1.79 – 1.61 (m,
1
3
H). C NMR (75 MHz, CDCl ) δ = 213.14, 140.66, 134.41, 128.89, 126.95, 126.82, 117.74,
3
+
6.95, 45.12, 40.23, 34.81, 28.35, 21.65. HRMS m/z calcd. for C H O [M + H]
1
5
19
1
15.14304; found 215.14308. The enantiomeric ratio was determined by HPLC using
Chiralcel OD-H column (Heptane/IPA : 99.9/0.1, 0.8 mL/min, 210 nm, t = 9.9 min (61.24
R
%
), t = 10.7 min (38.76 %)).
R

2- allyl-2-p-tolylcyclohexanone (5i)
1
Prepared according to the general procedure described above. H NMR
300 MHz, CDCl ) δ = 7.15 (d, J = 8.3 Hz, 2H), 7.03 (d, J = 8.3 Hz, 2H),
O
(
3
5
2
.59 – 5.27 (m, 1H), 5.08 – 4.75 (m, 2H), 2.63 (dd, J = 14.0, 2.7 Hz, 1H),
.54 – 2.37 (m, 2H), 2.37 – 2.20 (m, 5H), 1.95 – 1.87 (m, 1H), 1.82 – 1.54
1
3
(
m, 4H). C NMR (75 MHz, CDCl ) δ = 213.22, 137.54, 136.30, 134.47, 129.49, 126.72,
3
1
17.50, 56.44, 45.01, 40.03, 34.72, 28.22, 21.54, 20.94. HRMS m/z calcd. for C H O [M +
16 21 1
+
H] 229.15885; found 229.15869. The enantiomeric ratio was determined by HPLC using
Chiralcel OD-H column (Heptane/IPA : 99.9/0.1, 0.8 mL/min, 210 nm, t = 8.26 min (62.12
R
%
), t = 8.93 min (37.88 %)).
R

2- allyl-2-(4-fluorophenyl)cyclohexanone (5j)
1
Prepared according to the general procedure described above. H NMR
300 MHz, CDCl ) δ = 7.19 – 6.92 (m, 4H), 5.41 (ddt, J = 10.2, 7.8, 7.4
O
F
(
3
Hz, 1H), 5.05 – 4.75 (m, 2H), 2.65 – 2.54 (m, 1H), 2.53 – 2.34 (m, 2H),
1
3
2
.35 – 2.19 (m, 2H), 2.04 – 1.84 (m, 1H), 1.79 – 1.54 (m, 4H). C NMR
(
75 MHz, CDCl ) δ = 212.71, 161.56 (d, J = 246.0 Hz), 136.21 (d, J = 3.2 Hz), 133.94,
3
1
2
2
28.48 (d, J = 7.8 Hz), 117.93, 115.62 (d, J = 21.2 Hz), 56.29, 44.95, 39.97, 34.88, 28.14,
1
9
+
1.45. F NMR (282 MHz, CDCl ) δ = -116.00. HRMS m/z calcd. for C H F O [M + H]
3
15 18
1
1
33.13378; found 233.13362. The enantiomeric ratio was determined by HPLC using
Chiralcel OD-H column (Heptane/IPA : 99.9/0.1, 0.8 mL/min, 210 nm, t = 9.141 min (59.42
R
%
), t = 9.697 min (40.58 %)).
R
S-14


2- allyl-2-phenylcyclopentanone (5k)
1
Prepared according to the general procedure described above. H NMR (300
O
Ph
MHz, CDCl ) δ = 7.46 – 7.37 (m, 2H), 7.37 – 7.27 (m, 2H), 7.28 – 7.17 (m, 1H),
3
5
.50 (ddt, J = 19.7, 9.5, 7.3 Hz, 1H), 5.11 – 4.84 (m, 2H), 2.66 – 2.49 (m, 2H),
1
3
2
.49 – 2.42 (m, 1H), 2.35 – 2.23 (m, 2H), 2.16 – 2.05 (m, 1H), 2.00 – 1.74 (m, 2H). C NMR
(
75 MHz, CDCl ) δ = 219.11, 139.57, 133.98, 128.50, 126.80, 118.00, 56.48, 43.29, 37.66,
3
+
3
3.25, 18.55. HRMS m/z calcd. for C H O [M + H] 201.12744; found 201.12739. The
14
17
1
enantiomeric ratio was determined by HPLC using Chiralcel OJ-H column (Heptane/EtOH :
8/2, 0.8 mL/min, 210 nm, t = 10.433 min (40.37 %), t = 12.622 min (59.63 %)).
9
R
R
II.4. Sequential and mechanistic tests
General Procedure for the Sequential Catalysis Testing on D-(+)-Carvone
Preparation of the Silyl Enolate (in situ)
-
A flame-dried Schlenk was charged sequentially with the copper catalyst (10.2 mg, 0.02
mmol, 0.02 eq.), t-BuOK (2.4 mg, 0.02 mmol, 0.02 eq.) and 1 mL of the designated solvent
o
(
THF or toluene). Carvone was then added (153.3 mg, 1 mmol, 1 eq.) at 0 C, followed by the
silane (1.7 mmol, 1.7 eq.). The reaction was monitored by TLC and after total consumption of
the starting materiel (1hour), the reaction mixture was used in the next step without any
further purification.
-
Sequential Allylation Reaction
A flame-dried Schlenk was charged sequentially with the indicated amount of the palladium
complex, dppe (0.1 mmol, 0.1 eq.) and 0.5 mL of the indicated solvent. The reaction mixture
was stirred at room temperature. After 5 minutes the tert-butyl allylcarbonate (1.5 mmol, 1.5
eq.) was added, followed by the additive (if indicated) and the mixture was stirred for an
additional 5 minutes. The silyl enolate solution obtained above was then transferred to the
o
o
palladium solution at the indicated temperature (65 C or 45 C). After 24 hours, 1.4 mL of
TBAF (1M in THF) was added to the reaction mixture followed by a saturated aqueous
solution of NH Cl and Et O. The two phases were then separated and the aqueous layer was
4
2
extracted three times with Et O. The combined organic layers were dried over MgSO and
2
4
concentrated in vacuo. The residue was purified by column chromatography (petroleum ether/
Et O, 96/4) to give the two diastereoisomers of the desired product.
2
S-15

General Procedure for the C-alkylation vs O-alkylation Testing on D-(+)-Carvone
Preparation of the O-alkylated product 2
-
A flame-dried Schlenk was charged sequentially with palladium acetate (0.005 mmol, 0.01
eq.), dppe (0.0125 mmol, 0.025 eq.) and 0.5 mL of THF. The reaction mixture was stirred at
room temperature. After 5 minutes, methyl allylcarbonate (1 mmol, 2 eq.) was added and the
mixture was stirred for an additional 5 minutes. Simultaneously, another flame-dried Schlenk
was charged with IMesCuDBM (0.025 mmol, 0.05 eq.) in 0.5 mL of THF. Once the
palladium acetate was totally dissolved, the palladium mixture was transferred into the
Schlenk containing the copper catalyst followed immediately by the Carvone (0.5 mmol, 1
eq.). Me(EtO) SiH (0.85 mmol, 1.7 eq.) was then quickly added. The reaction mixture was
2
then stirred at room temperature. After 24 hours, 1.4 mL of TBAF (1M in THF) was added to
the reaction mixture. The latter was then filtered on a plug silica gel (eluting with petroleum
ether/Et O, 4/1). The filtrate was concentrated in vacuo to obtain a colourless residue. The
2
residue was purified by column chromatography (petroleum ether/Et O, 96/4) to give the
2
desired product 2 in 63% yield.

(S)- 2-(allyloxy)-1-methyl-4-(prop-1-en-2-yl)cyclohex-1-ene (2)
1
H NMR (300 MHz, CDCl ) δ = 5.88 (ddd, J = 22.7, 11.0, 5.8 Hz, 1H),
3
O
5
.42 – 5.19 (m, 2H), 4.79 – 4.68 (m, 2H), 4.68 – 4.58 (m, 2H), 2.65 – 2.42
(m, 3H), 2.39 – 2.26 (m, 1H), 1.92 – 1.76 (m, 1H), 1.70 (s, 3H), 1.67 –
1
3
1
.59 (m, 1H), 1.52 – 1.37 (m, 1H), 1.30 (s, 3H). C NMR (75 MHz,
CDCl ) δ = 207.28, 172.58, 147.13, 131.39, 119.12, 109.99, 65.84, 56.39, 46.63, 45.74, 37.01,
3
+
2
8.09, 21.11. HRMS m/z calcd. for C H O [M + H] 193.15869; found 193.15891.
1
3
21
1
-
Rearrangement Tests on Substrate 2
A flame-dried Schlenk was charged sequentially with the palladium acetate (0.005 mmol,
.01 eq.), the indicated phosphine (0.0125 mmol, 0.025 eq.) and 0.4 mL of toluene. The
0
reaction mixture was stirred at room temperature. After 5 minutes, methyl allylcarbonate (if
indicated, 1 mmol, 1 eq.) was added and the mixture was stirred for an additional 5 minutes.
Simultaneously, another flame-dried Schlenk was charged with IMesCuDBM (0.025 mmol,
0
.05 eq.) in 0.4 mL of toluene. Once the palladium acetate was totally dissolved, the
palladium mixture was transferred into the Schlenk containing the copper catalyst followed
immediately by substrate 2 (0.5 mmol, 1. eq., diluted in 0.2 mL of toluene). The mixture was
S-16

then immediately put at the indicated temperature. After 24 hours, 0.7 mL of TBAF (1M in
THF) was added to the reaction mixture. The latter was then filtered on a plug silica gel
(
eluting with petroleum ether/Et O, 4/1). The filtrate was concentrated in vacuo to obtain a
2
colourless residue. A sample of this residue was taken for GC and NMR analysis.
General Procedure for the mechanistic testing on substrate 4a
-
Formation of the Silyl Enol Ether 4a’
A flame-dried Schlenk was charged sequentially with IMesCuDBM (15 mg, 0.025 mmol,
0
.05 eq.), t-BuOK (5.8 mg, 0.05 mmol, 0.1 eq.) and 1 mL of toluene. Substrate 4a (75 mg, 0.5
o
mmol, 1 eq.) was then added at 0 C, followed by Me(EtO) SiH (0.14 mL, 0.85 mmol, 1.7
2
eq.). The reaction was monitored by TLC and after total consumption of the starting materiel
(
1hour), the mixture was filtered on a plug silica gel (eluting with petroleum ether/Et O, 4/1).
2
The filtrate was concentrated in vacuo to obtain a colourless residue.
The obtained residue was a mixture of two inseparable silyl enols. Therefore this residue was
not purified any further and was later hydrolysed to make sure that the reaction was complete
and to confirm the observation of the reduction product. This residue (4a’) was used directly
in the subsequent allylation tests, and this procedure was repeated for each sequential test.
Hydrolysis of enolate 4a’ in the presence of TBAF (0.8 mL, 0.8 mmol, 1.6 eq., 1M soln. in
THF) gave a quantitative yield of the reduction product 7.

2- butylcyclohexanone (7)
1
H NMR (300 MHz, CDCl ) δ = 2.44 – 2.18 (m, 3H), 2.17 – 1.94 (m, 2H),
3
O
n-Bu
13
1
.91 – 1.54 (m, 4H), 1.48 – 1.10 (m, 6H), 0.88 (t, J = 6.9 Hz, 3H). C NMR
(
75 MHz, CDCl ) δ = 213.67, 50.77, 41.96, 33.83, 29.41, 29.12, 28.05, 24.81,
3
2
2.84, 14.02.
Spectral data are identical to those reported in the literature.
Allylation Tests on Substrate 4a’
7
-
7
C. F. Malosh, J. M. Ready, J. Am. Chem. Soc. 2004, 126, 10240.
S-17

A flame-dried Schlenk was charged sequentially with the palladium acetate (0.005 mmol,
.01 eq.), the indicated phosphine (0.0125 mmol, 0.025 eq.) and 0.4 mL of toluene. The
0
reaction mixture was stirred at room temperature. After 5 minutes, methyl allylcarbonate (1
mmol, 1 eq.) was added and the mixture was stirred for an additional 5 minutes.
Simultaneously, another flame-dried Schlenk was charged with the copper catalyst (if
indicated, 0.025 mmol, 0.05 eq.) and the appropriate amount of additives (if indicated) in 0.4
mL of toluene and stirred for 1 minute. Once the palladium acetate was totally dissolved, the
palladium mixture was transferred into the Schlenk containing the copper catalyst followed
immediately by the above obtained residue 4a’ (0.5 mmol, 1. eq., diluted in 0.2 mL of
o
toluene). The mixture was then immediately put at 45 C. After 24 hours, 0.7 mL of TBAF
(1M in THF) was added to the reaction mixture. The latter was then filtered on a plug silica
gel (eluting with petroleum ether/Et O, 4/1). The filtrate was concentrated in vacuo to obtain a
2
colorless residue. A sample of this residue was taken for GC and NMR analysis.

DBM(allyl)2
1
H NMR (300 MHz, CDCl ) δ = 7.94 – 7.73 (m, 4H), 7.49 – 7.39 (m, 2H),
3
O
O
7
2
.39 – 7.29 (m, 4H), 5.48 (ddt, J = 17.5, 10.1, 7.5 Hz, 2H), 5.10 – 4.98 (m,
Ph
Ph
1
3
H), 4.90 (dd, J = 16.9, 1.8 Hz, 2H), 2.97 (d, J = 7.5 Hz, 4H). C NMR (75
MHz, CDCl ) δ = 198.61, 136.33, 133.14, 131.60, 128.97, 128.72, 119.67,
3
6
6.44, 37.53.
Spectral data are identical to those reported in the literature.
Preparation of the DBM(Me)2
8
-
A flame-dried round-bottomed flask was charged with DBM (1.121 g, 5 mmol, 1 eq.) in 70
mL of a mixture of DMSO/CHCl (53/17). K CO (4.146 g, 30 mmol, 6 eq.) was added to the
3
2
3
mixture, followed by MeI (1.25 mL, 20 mmol, 4 eq.). The reaction mixture was stirred at
room temperature for 3 days, after which MTBE (50 mL) was added, and the solution was
8
R. Grigg, J. F. Malone, T. R. B. Mitchell, A. Ramasubbu, R. M. Scott, Journal of the Chemical Society, Perkin
Transactions 1 1984, 1745.
S-18

stirred for an additional 30 minutes. The mixture was filtered over celite, washed three times
with water, dried over MgSO , filtered and concentrated in vacuo to afford the desired
4
product DBM(Me) (0.95 g, 75%).
2

DBM(Me)2
1
H NMR (300 MHz, CDCl ) δ = 8.28 – 8.05 (m, 4H), 7.82 – 7.72 (m, 2H),
3
O
O
Ph
Ph
7.65 (dd, J = 8.2, 6.9 Hz, 4H), 2.00 (s, 6H).
9
Spectral data are identical to those reported in the literature.
III. α,β-unsaturated malonates:
III.1. Preparation of the starting materials 8a-j
General procedure for the preparation of 8a :
To a stirred solution of methyl 2-cyanoacetate (995.4 mg, 10 mmol, 1.0 eq.) and
benzaldehyde (1.1 mL, 10.8 mmol, 1.1 eq.) was added 3 g of neutral Al O . The reaction was
2
3
very exothermic. After 5 min, DCM was added and the solution was filtered. Water was
added to the filtrate and the two phases were then separated. The aqueous layer was extracted
three times with DCM. The combined organic layers were dried over MgSO , filtered and
4
concentrated in vacuo. The solid was recrystallised in hot isopropanol to obtain pure 8a as a
white solid (1.64 g, 87%).

(E)-methyl 2-cyano-3-phenylacrylate (8a)
1
H NMR (300 MHz, CDCl ) δ = 8.27 (s, 1H), 8.15 – 7.86 (m, 2H), 7.71 –
3
NC
CO Me
2
1
3
7
1
.39 (m, 3H), 3.94 (s, 3H). C NMR (75 MHz, CDCl ) δ = 163.05,
3
55.40, 133.47, 131.41, 131.16, 129.34, 115.50, 102.54, 53.46.
9
E. Volker Dehmlow, M. Kaiser, J. Bollhöfer, New J. Chem. 2001, 25, 588.
S-19

1
0
Spectral data are identical to those reported in the literature.
General procedure for the preparation of 8b-i :
To a solution of the aldehyde (5 mmol, 1.0 eq.) in methanol (5 mL) were added methyl 2-
cyanoacetate or malonitrile (5.5 mmol, 1.1 eq.) and five drops of both acetic acid and
piperidine. Within 5 minutes, a white solid started to precipitate from the reaction mixture
which was stirred 4h-5h at room temperature. The solid was then filtered, washed with hexane
and dried in vacuo to afford the desired product.

(E)-methyl 2-cyano-3-(4-methoxyphenyl)acrylate (8b)
The general procedure afforded the desired product white solid (830
NC
CO Me
2
1
mg, 76% yield). H NMR (300 MHz, CDCl ) δ = 8.18 (s, 1H), 8.00
3
(
d, J = 8.9 Hz, 2H), 7.04 – 6.95 (d, J = 8.9 Hz, 2H), 3.92 (s, 3H),
MeO
1
3
3
.89 (s, 3H). C NMR (75 MHz, CDCl ) δ = 164.02, 163.79,
3
1
54.82, 133.86, 124.45, 116.35, 114.94, 99.00, 55.78, 53.35.
1
0
Spectral data are identical to those reported in the literature.
(E)-methyl 2-cyano-3-(o-tolyl)acrylate (8c)

The general procedure afforded the desired product white solid (565.9 mg,
NC
CO Me
2
1
5
6% yield). H NMR (300 MHz, CDCl ) δ = 8.58 (s, 1H), 8.15 (d, J = 7.7
3
Hz, 1H), 7.43 (t, J = 7.5 Hz, 1H), 7.35 – 7.28 (m, 2H), 3.95 (s, 3H), 2.46
s, 3H). C NMR (75 MHz, CDCl ) δ = 163.06, 153.70, 139.90, 133.00, 131.13, 130.60,
1
3
(
3
1
28.71, 126.83, 115.45, 104.11, 53.52, 19.97
Spectral data are identical to those reported in the literature.
(E)-methyl 2-cyano-3-(4-fluorophenyl)acrylate (8d)
1
0

10
S. Sö1rgel, N. Tokunaga, K. Sasaki, K. Okamoto, T. Hayashi, Org. Lett. 2008, 10, 589.
S-20

The general procedure afforded the desired product white solid (700.2
NC
CO Me
2
1
mg, 68% yield). H NMR (300 MHz, CDCl ) δ = 8.23 (s, 1H), 8.06 –
3
1
3
8
.01 (m, 2H), 7.20 (t, J = 8.6 Hz, 2H), 3.94 (s, 3H). C NMR (75 MHz,
F
CDCl ) δ = 165.59 (d, J = 257.8 Hz), 163.03, 153.90, 133.78 (d, J = 9.2
3
19
Hz), 127.90 (d, J = 3.2 Hz), 116.87 (d, J = 22.1 Hz), 115.53, 102.23, 53.59. F NMR (282
MHz, CDCl ) δ = -104.05.
3
1
1
Spectral data are identical to those reported in the literature.

(E)-methyl 2-cyano-3-(4-(trifluoromethyl)phenyl)acrylate (8e)
The general procedure afforded the desired product white solid (997
NC
CO Me
2
1
mg, 78% yield). H NMR (300 MHz, CDCl ) δ = 8.29 (s, 1H), 8.09
3
1
3
(
d, J = 8.4 Hz, 2H), 7.77 (d, J = 8.3 Hz, 2H), 3.97 (s, 3H). C NMR
F3C
(
75 MHz, CDCl ) δ = 162.42, 153.38, 134.59, 134.16, 131.17, 126.36
3
1
9
(
d, J=3.7), 123.46 (q, J=271.5 Hz), 114.91, 105.57, 53.82. F NMR (282 MHz, CDCl ) δ = -
3
6
4.67.
1
2
Spectral data are identical to those reported in the literature.

(E)-methyl 2-cyano-3-(4-cyanophenyl)acrylate (8f)
The general procedure afforded the desired product white solid (871.8
NC
CO Me
2
1
mg, 82% yield). H NMR (300 MHz, CDCl ) δ = 8.26 (s, 1H), 8.06
3
1
3
(
d, J = 8.3 Hz, 2H), 7.80 (d, J = 8.5 Hz, 2H), 3.97 (s, 3H). C NMR
NC
(
75 MHz, CDCl ) δ = 162.15, 152.64, 135.24, 132.98, 131.15, 117.78,
3
1
16.21, 114.68, 106.40, 53.92.
1
2
Spectral data are identical to those reported in the literature.

(E)-methyl 2-cyano-3-(pyridin-4-yl)acrylate (8g)
The general procedure afforded the desired product white solid (417.4
NC
CO Me
2
1
mg, 44% yield). H NMR (300 MHz, CDCl ) δ = 8.82 (d, J = 6.0 Hz,
3
1
3
N
2H), 8.20 (s, 1H), 7.76 (d, J = 6.0 Hz, 2H), 3.96 (s, 3H). C NMR (75
1
1
1
2
C. Unaleroglu, D. I. Tasgin, S. Aytac, B. Temelli, Synthesis 2009, 19, 3243.
X. Yang, T. Fox, J. Berke, Org. Biomol. Chem. 2012, 10, 852.
S-21

MHz, CDCl ) δ = 161.86, 152.39, 151.01, 138.30, 123.49, 114.29, 108.11, 53.98.
3
1
3
Spectral data are identical to those reported in the literature.
(E)-methyl 2-cyano-3-cyclohexylacrylate (8h)

The general procedure was modified: reaction run overnight and then the
solvents were evaporated and the remaining residue was purified by flash
chromatography (petroleum ether/AcOEt, 95:5 to petroleum ether/AcOEt,
NC
CO Me
2
-
1
1
2
:1) to afford the desired product as a white solid (193.11 mg, 53% yield). IR (cm ) : 3009,
1
928, 2854, 2230, 1732, 1622, 1448, 1437, 1302, 1261, 1232. H NMR (300 MHz, CDCl ) δ
3
=
7.49 (d, J = 10.5 Hz, 1H), 3.85 (s, 3H), 2.76 – 2.64 (m, 1H), 1.86 – 1.66 (m, 4H), 1.45 –
1
3
1
5
.12 (m, 6H). C NMR (75 MHz, CDCl ) δ = 168.38 (s), 162.21 (s), 113.85 (s), 107.29 (s),
3
3.23 (s), 41.28 (s), 31.22 (s), 25.48 (s), 24.93 (s). HRMS m/z calcd. for C H NO Na [M +
1
1
15
2
1
+
Na] 216.09950, found 216.09961.

2-(4-methoxybenzylidene)malononitrile (8i)
1
H NMR (300 MHz, CDCl ) δ = 7.91 (d, J = 8.9 Hz, 2H), 7.65 (s, 1H),
3
NC
CN
1
3
7
1
.01 (d, J = 9.0 Hz, 2H), 3.92 (s, 3H). C NMR (75 MHz, CDCl ) δ =
3
64.91, 158.99, 133.54, 124.07, 115.21, 114.54, 113.46, 78.49, 55.90.
MeO
1
4
Spectral data are identical to those reported in the literature.
General procedure for the preparation of 8i :
To a solution of salicylaldehyde (1.05 mL, 10 mmol, 1.0 eq.) in DMF (15 mL) at 0 °C was
added imidazole (1.37g, 20 mmol, 2 eq.). Tert-butyldimethylsilyl chloride (1.75g, 11.5 mmol,
1
.15 eq.) in 5 mL DMF was added dropwise and the reaction mixture was stirred overnight at
room temperature. Et O (60 mL) and a half-saturated aqueous NaHCO solution (30 mL)
2
3
13
D. Blanco-Ania, C. Valderas-Cortina, H. W. Scheeren, F. P. J. T. Rutjes, P. H. H. Hermkens, L. A. J. M.
Sliedregt, Molecules 2010, 15, 226.
14
A. P. Dieskau, M. S. Holzwarth, B. Plietker, Chem. Eur. J. 2012, 18, 2423.
S-22

were added to the solution. The layers were separated, and the aqueous layer was extracted
with 2x30mL Et O. The organic layers were then successively washed with half-saturated
2
aqueous NH Cl solution, 10% aqueous LiCl solution (twice), water and brine. They were then
4
dried over MgSO and concentrated in vacuo. The obtained colourless liquid was dried in
4
vacuo to afford the desired product with the required purity for the next step (2.367 g,
quantitative).
1
H NMR (300 MHz, CDCl ) δ = 10.47 (s, 1H), 7.81 (dd, J = 7.8, 1.9 Hz, 1H), 7.49 –7.44 (m,
3
1
3
1
H), 7.02 (t, J = 7.5 Hz, 1H), 6.88 (d, J = 8.3 Hz, 1H), 1.02 (s, 9H), 0.28 (s, 6H). C NMR
75 MHz, CDCl ) δ = 190.24, 159.02, 135.81, 128.45, 127.36, 121.58, 120.33, 25.78, 18.47, -
(
3
4
.19.
To a solution of the above synthesized aldehyde (1.18 g, 5 mmol, 1.0 eq.) in methanol (5 mL)
were added methyl 2-cyanoacetate (0.49 mL, 5.5 mmol, 1.1 eq.) and five drops of both acetic
acid and piperidine (871.8 mg, 82% yield). The reaction mixture was stirred 3h30 at room
temperature. Water and Et O were added to the reaction mixture, and the layers were
2
separated. The aqueous layer was extracted twice with Et O. The organic layers were then
2
washed with water and brine, dried over MgSO and concentrated in vacuo. The obtained
4
residue was purified by flash chromatography (petroleum ether/Et O, 9:1) to afford the
2
desired product as an orange solid (1.075 g, 68% yield).

2-((tert-butyldimethylsilyl)oxy)benzaldehyde (8j)
-1
IR (cm ) : 3074, 2955, 2928, 2856, 2222, 1732, 1597, 1479, 1458, 1364,
NC
CO Me
2
1
1
308, 1252. H NMR (300 MHz, CDCl ) δ = 8.79 (s, 1H), 8.35 (dd, J =
3
8
1
.0, 1.6 Hz, 1H), 7.43 (ddd, J = 8.3, 7.4, 1.7 Hz, 1H), 7.07 (t, J = 7.7 Hz,
OTBS
1
3
H), 6.89 (d, J = 8.3 Hz, 1H), 3.92 (s, 3H), 1.04 (s, 9H), 0.26 (s, 6H). C
NMR (75 MHz, CDCl ) δ = 163.40, 156.73, 150.48, 135.10, 129.36, 123.29, 121.97, 119.83,
3
+
1
3
15.98, 101.36, 53.32, 25.73, 18.38, -4.23. HRMS m/z calcd. for C H NO Si [M + H]
17 24 3
18.15200, found 318.15214.
S-23

III.2. General procedure for the dual catalysis reaction
A flame-dried Schlenk was charged sequentially with palladium acetate (1.2 mg, 0.005 mmol,
0
.01 eq.) and Me -PHOX (4.5 mg, 0.0125 mmol, 0.025 eq.) in THF (0.4) mL, under argon
2
atmosphere. The mixture was stirred until dissolution of the substrates (5 min.).
Allylcarbonate (0.12 mL, 1 mmol, 2 eq.) was added and the solution was stirred at room
temperature. Simultaneously, another flame-dried Schlenk was charged with IMesCuDBM
(15.0 mg, 0.025 mmol, 0.05 eq.) in THF (0.4 mL). The palladium solution was then
transferred to the copper-containing Schlenk. The substrate 8a-j (0.5 mmol, 1 eq.) dissolved
in the minimum amount of THF (0.4-0.8 mL) was immediately added to the reaction mixture,
followed by the silane (0.14 mL, 0.85 mmol, 1.7 eq.). The reaction mixture was stirred 24h at
2
5 °C. A 1M TBAF solution in THF (0.7 mL, 0.7 mmol) was added to the mixture (except for
8
j), and after 5 minutes a 2 mL mixture of petroleum ether/AcOEt (1:1) was added. The
obtained mixture was filtered on a pad of silica (eluting with petroleum ether/AcOEt, 1:1),
and concentrated in vacuo. The crude product was purified by flash chromatography.

Methyl 2-benzyl-2-cyanopent-4-enoate (9a)
The general procedure yielded after flash chromatography on silica gel
COOMe
NC
(petroleum ether/AcOEt, 95:5) the desired product as a coulourless oil
-1
(
95.1 mg, 83% yield). IR (cm ) : 3032, 2955, 2924, 2852, 2245, 1744,
1
1
497, 1275, 1236. H NMR (300 MHz, CDCl ) δ = 7.43 – 7.21 (m, 5H),
3
5
1
1
1
2
.85 (ddt, J = 19.2, 9.8, 7.3 Hz, 1H), 5.30 – 5.24 (m, 2H), 3.68 (s, 3H), 3.21 (d, J = 13.5 Hz,
H), 3.07 (d, J = 13.5 Hz, 1H), 2.75 (dd, J = 13.7, 7.4 Hz, 1H), 2.58 (dd, J = 13.7, 7.1 Hz,
1
3
H). C NMR (75 MHz, CDCl ) δ = 168.74, 134.14, 130.64, 130.01, 128.77, 128.08, 121.29,
3
2
3
+
18.56, 53.36, 51.53, 42.71, 41.49. HRMS m/z calcd. for C H NO Na [M + Na]
14
15
2
1
52.09950, found 252.09941.

Methyl 2-cyano-2-(4-methoxybenzyl)pent-4-enoate (9b)
S-24

The general procedure yielded after flash chromatography on silica
gel (petroleum ether/AcOEt, 85:15) the desired product as a yellow
COOMe
NC
-1
oil (101.2 mg, 78% yield). IR (cm ) : 3005, 2956, 2852, 2245, 1744,
MeO
1
1
643, 1612, 1441, 1344, 1296. H NMR (300 MHz, CDCl ) δ = 7.22
3
–
2
7.14 (m, 2H), 6.88 – 6.81 (m, 2H), 5.83 (ddt, J = 18.8, 9.7, 7.3 Hz, 1H), 5.32 – 5.19 (m,
H), 3.79 (s, 3H), 3.69 (s, 3H), 3.09 (dd, J = 43.6, 13.7 Hz, 2H), 2.64 (ddd, J = 48.9, 13.8, 7.3
13
Hz, 2H). C NMR (75 MHz, CDCl ) δ = 168.64, 159.23, 130.90, 130.53, 125.94, 120.98,
3
23
1
18.50, 113.95, 55.16, 53.16, 51.61, 41.81, 41.17. HRMS m/z calcd. for C H NO Na [M
15 17 3 1
+
+
Na] 282.11006, found 282.11003.
Methyl 2-cyano-2-(2-methylbenzyl)pent-4-enoate (9c)
The general procedure yielded after flash chromatography on silica gel

COOMe
NC
(petroleum ether/AcOEt, 95:5) the desired product as a coulourless oil
-1
(
97.4 mg, 79% yield). IR (cm ) : 2955, 2924, 2853, 2245, 1742, 1643,
1
1
497, 1435, 1346, 1236. H NMR (300 MHz, CDCl ) δ = 7.24 – 7.10 (m,
3
4
H), 5.96 – 5.77 (m, 1H), 5.31 – 5.25 (m, 2H), 3.72 (s, 3H), 3.23 (d, J = 1.3 Hz, 2H), 2.80
1
3
(
dd, J = 13.6, 7.4, 1H), 2.61 (dd, J = 13.7, 7.2, 1H), 2.40 (s, 3H). C NMR (75 MHz, CDCl )
3
δ = 169.13, 137.28, 132.71, 131.09, 130.69, 130.14, 128.00, 126.21, 121.35, 118.71, 53.43,
+
5
2
0.89, 41.78, 38.89, 19.98. HRMS m/z calcd. for C H NO [M + H] 244.13321, found
1
5
18
2
44.13317.

Methyl 2-cyano-2-(4-fluorobenzyl)pent-4-enoate (9d)
The general procedure yielded after flash chromatography on silica gel
petroleum ether/AcOEt, 95:5 to 93:7) the desired product as a
COOMe
NC
(
-1
coulourless oil (97.4 mg, 79% yield). IR (cm ) : 2955, 2924, 2853,
F
1
2
245, 1744, 1643, 1605, 1510, 1443, 1221. H NMR (300 MHz, CDCl )
3
δ = 7.33 – 7.18 (m, 2H), 7.17 – 6.92 (m, 2H), 5.96 – 5.72 (m, 1H), 5.39 – 5.17 (m, 2H), 3.69
(s, 3H), 3.19 (d, J = 13.7 Hz, 1H), 3.04 (d, J = 13.7 Hz, 1H), 2.74 (dd, J = 13.7, 7.4 Hz, 1H),
1
3
2
1
5
.58 (dd, J = 13.7, 7.1 Hz, 1H). C NMR (75 MHz, CDCl ) δ = 168.62, 162.66 (d, J = 246.7),
3
31.64 (d, J = 8.2), 130.46, 129.95 (d, J = 3.2 Hz), 121.41, 118.44, 115.72 (d, J = 21.5),
1
9
3.42, 51.58, 41.81, 41.53. F NMR (282 MHz, CDCl ) δ = -115.53. HRMS m/z calcd. for
3
+
C H FNO [M + H] 248.10813, found 248.10809.
14
15
2

Methyl 2-cyano-2-(4-(trifluoromethyl)benzyl)pent-4-enoate (9e)
S-25

The general procedure yielded after flash chromatography on silica gel
petroleum ether/AcOEt, 95:5 to 9:1) the desired product as a
COOMe
NC
(
-1
coulourless oil (64.0 mg, 43% yield). IR (cm ) : 2922, 2853, 2247,
F3C
1
1
620, 1438, 1421, 1325, 1238. H NMR (300 MHz, CDCl ) δ = 7.59
3
(
d, J = 8.1 Hz, 2H), 7.40 (d, J = 8.1 Hz, 2H), 5.83 (ddd, J = 14.6, 9.6, 7.3 Hz, 1H), 5.35 – 5.14
m, 2H), 3.70 (s, 3H), 3.27 (d, J = 13.5 Hz, 1H), 3.11 (d, J = 13.5 Hz, 1H), 2.76 (dd, J = 13.7,
(
1
3
7
1
4
.5 Hz, 1H), 2.60 (dd, J = 13.7, 7.2 Hz, 1H). C NMR (75 MHz, CDCl ) δ = 168.42, 138.22,
3
30.62, 130.44, 130.23, 125.93, 125.74 (d, J=3.7), 122.32, 121.68, 118.20, 53.55, 51.21,
1
9
2.09, 41.75. F NMR (282 MHz, CDCl ) δ = -63.75. HRMS m/z calcd. for C H F NO
2
3
15 14
3
2
3
+
Na [M + Na] 320.08688, found 320.08701.
1

Methyl 2-cyano-2-(4-cyanobenzyl)pent-4-enoate (9f)
The general procedure yielded after flash chromatography on silica gel
COOMe
NC
(petroleum ether/AcOEt, 8:2) the desired product as a coulourless oil
-1
(
76.5 mg, 60% yield). IR (cm ) : 2955, 2922, 2853, 2230, 1744, 1609,
NC
1
1
437. H NMR (300 MHz, CDCl ) δ = 7.62 (d, J = 8.3 Hz, 2H), 7.39
3
(d, J = 8.3 Hz, 2H), 5.92 – 5.73 (m, 1H), 5.30 – 5.24 (m, 2H), 3.68 (s, 3H), 3.27 (d, J = 13.5
Hz, 1H), 3.09 (d, J = 13.5 Hz, 1H), 2.75 (dd, J = 13.7, 7.4 Hz, 1H), 2.60 (dd, J = 13.7, 7.2 Hz,
1
3
1
1
H). C NMR (75 MHz, CDCl ) δ = 168.17, 139.58, 132.48, 130.82, 130.01, 121.79, 118.53,
3
23
17.96, 112.16, 53.58, 51.01, 42.12, 41.77. HRMS m/z calcd. for C H N O Na [M +
15
14
2
2
1
+
Na] 277.09475, found 277.09478.

Methyl 2-cyano-2-(pyridin-4-ylmethyl)pent-4-enoate (9g)
The general procedure yielded after flash chromatography on silica gel
COOMe
NC
1
(
AcOEt) the desired product as a coulourless oil (45 mg, 40% yield). H
NMR (300 MHz, CDCl ) δ = 8.60 (br, 2H), 7.22 (br, 2H), 5.95 – 5.72 (m,
3
N
1
H), 5.38 – 5.21 (m, 2H), 3.70 (s, 3H), 3.20 (d, J = 13.5 Hz, 1H), 3.04 (d,
1
3
J = 13.5 Hz, 1H), 2.76 (dd, J = 13.7, 7.4 Hz, 1H), 2.61 (dd, J = 13.7, 7.1 Hz, 1H). C NMR
75 MHz, CDCl ) δ = 168.21, 150.24, 143.12, 130.03, 125.17, 121.86, 118.00, 53.62, 50.59,
(
3
4
1.86, 41.51.

Methyl 2-cyano-2-(cyclohexylmethyl)pent-4-enoate (9h)
S-26

The general procedure yielded after flash chromatography on silica gel
COOMe
NC
(petroleum ether/AcOEt, 98:2) the desired product as a coulourless oil
-1
(
95.8 mg, 81% yield). IR (cm ) : 3080, 2926, 2853, 2243, 1744, 1643,
1
1
448, 1304, 1227. H NMR (300 MHz, CDCl ) δ = 5.87 – 5.73 (m, 1H),
3
5
6
5
.28 – 5.14 (m, 2H), 3.79 (s, 3H), 2.64 – 2.46 (m, 2H), 1.91 – 1.80 (m, 2H), 1.73 – 1.47 (m,
1
3
H), 1.37 – 0.82 (m, 5H). C NMR (75 MHz, CDCl ) δ = 169.78, 130.70, 121.00, 119.17,
3
3.35, 48.57, 44.00, 43.17, 35.42, 33.89, 32.93, 26.12. HRMS m/z calcd. for C H NO [M +
1
5
22
2
+
H] 236.16451, found 236.16452.

2-allyl-2-(4-methoxybenzyl)malononitrile (9i)
The general procedure yielded after flash chromatography on silica
CN
NC
gel (petroleum ether/AcOEt, 98:2) the desired product as a yellow oil
1
(
97.2 mg, 86% yield). H NMR (300 MHz, CDCl ) δ = 7.30 (d, J =
3
MeO
8
.7 Hz, 2H), 6.93 (d, J = 8.7 Hz, 2H), 6.04 – 5.85 (m, 1H), 5.51 –
1
3
5
.32 (m, 2H), 3.82 (s, 3H), 3.15 (s, 2H), 2.69 (d, J = 7.2 Hz, 2H). C NMR (75 MHz, CDCl )
3
δ = 160.04, 131.47, 128.77, 123.99, 123.36, 115.12, 114.46, 55.37, 42.08, 41.27, 39.58.
+
HRMS m/z calcd. for C H N O [M + H] 227.11789, found 227.11803.
1
4
15
2

Methyl 2-(2-((tert-butyldimethylsilyl)oxy)benzyl)-2-cyanopent-4-enoate (9j)
The general procedure (without any TBAF addition at the end of the
COOMe
NC
reaction) yielded after flash chromatography on silica gel (petroleum
ether/AcOEt, 97:3) the desired product as a yellow oil (100 mg, 56%
OTBS
-1
yield). IR (cm ) : 3078, 2952, 2927, 2856, 2245, 1747, 1643, 1601, 1582,
1
1
493, 1454, 1256, 1238. H NMR (300 MHz, CDCl ) δ = 7.25 (dd, J = 7.6, 1.5 Hz, 1H), 7.17
3
(
td, J = 7.8, 1.8 Hz, 1H), 6.92 (td, J = 7.5, 1.1 Hz, 1H), 6.84 (dd, J = 8.1, 1.1 Hz, 1H), 5.82
ddt, J = 17.1, 9.6, 7.3 Hz, 1H), 5.23 (m, 2H), 3.74 (s, 3H), 3.34 (d, J = 13.6 Hz, 1H), 3.12 (d,
(
J = 13.6 Hz, 1H), 2.77 (dd, J = 13.8, 7.5 Hz, 1H), 2.49 (dd, J = 13.8, 7.1 Hz, 1H), 1.03 (s,
1
3
9
1
1
3
H), 0.27 (s, 3H), 0.29 (s, 3H). C NMR (75 MHz, CDCl ) δ = 169.12, 154.35, 131.28,
3
31.16, 129.03, 124.91, 121.26, 120.88, 118.72, 118.60, 53.35, 50.77, 40.84, 35.84, 26.03,
+
8.45, -3.96, -4.06.HRMS m/z calcd. for C H N O Si [M + H] 360.19895, found
2
0
30
1
3
1
60.19882.
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IV. Coumarines:
IV.1. Preparation of the starting materials 11a-b
General procedure for the preparation of 11a,b :
To a solution of the aldehyde (1.05 mL, 10 mmol, 1.0 eq.) in methanol (5 mL) were added
dimethylmalonate (1.67 mL, 14.6 mmol, 1.46 eq.) and five drops of both acetic acid and
piperidine. The reaction mixture was refluxed overnight. Water was added to the solution,
which was then cooled for one hour at 0 °C. The precipitate was filtrated, washed with
methanol and hexane and dried in vacuo to afford the desired product.

Methyl-2-oxo-2H-chromene-3-carboxylate (11a)
The general procedure afforded the desired product white solid (1.64 g,
COOMe
O
1
8
0% yield). H NMR (300MHz, CDCl ) δ = 8.58 (s, 1H), 7.69 – 7.61
3
O
1
3
(
m, 2H), 7.39 – 7.32 (m, 2H), 3.96 (s, 3H). C NMR (300MHz,
CDCl ) δ = 163.87, 156.86, 155.37, 149.32, 134.62, 129.70, 125.04, 118.08, 117.99, 116.96,
3
5
3.09.
1
5
Spectral data are identical to those reported in the literature.

Methyl 7-methoxy-2-oxo-2H-chromene-3-carboxylate (11b)
The general procedure afforded the desired product white solid
COOMe
O
1
(
2.34 g, 78% yield). H NMR (300 MHz, CDCl ) δ = 8.54 (s,
3
MeO
O
1
H), 7.50 (d, J = 8.7 Hz, 1H), 6.89 (dd, J = 8.7, 2.4 Hz, 1H), 6.82
13
(
d, J = 2.3 Hz, 1H), 3.94 (s, 3H), 3.90 (s, 3H). C NMR (75 MHz, CDCl ) δ = 165.40,
3
1
64.28, 157.79, 157.30, 149.65, 130.92, 113.89, 111.77, 100.49, 56.17, 52.88.
15
A. Leone-Bay et al, J. Med. Chem. 1998, 41, 1163.
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1
6
Spectral data are identical to those reported in the literature.
IV.2. General Procedure for the dual catalysis reaction
A flame-dried Schlenk was charged sequentially with palladium acetate (1.2 mg, 0.005 mmol,
.01 eq.) and Me -PHOX (4.5 mg, 0.0125 mmol, 0.025 eq.) in THF (0.4) mL, under argon
0
2
atmosphere. The mixture was stirred until dissolution of the substrates (5 min.).
Allylcarbonate (0.06 mL, 0.5 mmol, 1 eq.) was added and the solution was stirred at room
temperature. Simultaneously, another flame-dried Schlenk was charged with IMesCuDBM
(15.0 mg, 0.025 mmol, 0.05 eq.) in THF (0.4 mL). The palladium solution was then
transferred to the copper-containing Schlenk. The substrate 11a-c (1 mmol, 2 eq.) dissolved in
the minimum amount of THF (0.4-0.8 mL) was immediately added to the reaction mixture,
followed by the silane (0.10 mL, 0.60 mmol, 1.2 eq.). The reaction mixture was stirred 24h at
2
5 °C. TFA (0.05 mL, 0.7 mmol) was added to the mixture, which was then stirred 2 hours at
room temperature. A solution of 5% NaHCO3(aq) was added to the mixture, and the aqueous
layer was extracted three times with AcOEt. The organic layers were washed with brine, dried
over MgSO and concentrated in vacuo. The crude product was purified by flash
4
chromatography.

Methyl 3-allyl-2-oxochroman-3-carboxylate (13a)
The general procedure yielded after flash chromatography on silica gel
petroleum ether/AcOEt, 97:3) the desired product as a white solid (112
(
CO Me
2
-
1
mg, 91% yield). IR (cm ) : 3080, 2922, 2853, 1771, 1738, 1639, 1614,
O
O
1
1
589, 1489, 1458, 1435, 1344, 1229. H NMR (300 MHz, CDCl ) δ =
3
7
.30 – 6.96 (m, 4H), 5.89 (ddt, J = 17.4, 10.2, 7.3 Hz, 1H), 5.17 (m, 2H), 3.61(s, 3H), 3.30 (d,
1
3
J = 16.0 Hz, 1H), 3.04 (d, J = 16.0 Hz, 1H), 2.75 (d, J = 7.3 Hz, 2H). C NMR (75 MHz,
CDCl ) δ = 169.97, 166.96, 151.07, 131.96, 128.70, 128.47, 124.84, 121.19, 120.39, 116.56,
3
16
I. Yavari, H. Djahaniani, F. Nasiri, Synthesis 2004, 5, 679.
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