Asymmetric Ni-catalyzed conjugate allylation of activated enones

Article abstract of DOI:10.1021/ja710922h

The nickel-catalyzed enantioselective addition of allylboronic acid pinacol ester, allylB(pin), is described. This reaction is highly effective with dialkylidene ketones and favors the allylation of the benzylidene site in nonsymmetric substrates. The rea

Full text of DOI:10.1021/ja710922h

Asymmetric Ni-Catalyzed Conjugate Allylation of Activated Enones
*
Joshua D. Sieber and James P. Morken
Department of Chemistry, Merkert Chemistry Center
Boston College, Chestnut Hill, MA, 02467
Supplementary Material
Table of Contents
General
S-2
S-3
Ligand synthesis
Substrate synthesis
S-4
Conjugate allylation procedures
S-9
Conjugate allylation product manipulations
Conjugate allylation using substrate with tethered phosphino-directing group
Synthesis and characterization of Ni-enone complex
Labeling experiments…
S-33
S-34
S-37
S-42
S-42
S-44
Non-linear effects…
1
13
H and C NMR data…
Supporting Information Page S-1

General. Melting points were determined using a Mel-Temp II melting point apparatus and are
1
uncorrected. H NMR spectra were recorded on Gemini-500 (500 MHz), Gemini-400 (400 MHz), or Gemini-
3
00 (300 MHz) spectrometers. Chemical shifts are reported in ppm from tetramethylsilane with the solvent
resonance as an internal standard (CDCl : 7.24 ppm, C : 7.15 ppm). Data are reported as follows: chemical
6
D
6
3
shift, integration, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, h = hextet, br = broad,
m = multiplet), and coupling constants (Hz). 13C NMR was recorded on a Gemini-400 (100 MHz) instrument,
or a Gemini-500 (125 MHz) instrument with complete proton decoupling. Chemical shifts are reported in ppm
1
9
from tetramethylsilane with the solvent as the internal standard (CDCl : 77.0 ppm, C D : 128.39 ppm).
F
3
6
6
NMR was recorded on a Gemini-500 (470 MHz) instrument. Chemical shifts are reported in ppm and are
3
1
referenced to a 0.05% solution of C
MHz) instrument with complete proton decoupling. Chemical shifts are reported in ppm and are referenced to
5% H PO (0.0 ppm). Low-resolution mass spectrometry was performed by the Boston College, Department
6
F
6
(-63.72 ppm) in C
6
D
6
.
P NMR was recorded on a Gemini-300 (121
8
3
4
of Chemistry Mass Spectrometry Facility. Infrared (IR) spectra were obtained on a Nicolet 210
spectrophotometer. Optical rotations were measured using a Rudolf Research Analytical Autopol IV
Polarimeter.
Liquid chromatography was performed using forced flow (flash chromatography) on silica gel (SiO , 40-63
2
μm) purchased from Silicycle. Thin layer chromatography (TLC) was performed on 250 μm silica gel plates
from Silicycle or 200 μm neutral alumnia TLC plates from Sorbent Technologies. Visualization was achieved
using UV light, phosphomolybdic acid in ethanol, or potassium permanganate in water, each followed by
heating.
Analytical chiral gas-liquid chromatography (GLC) was performed on a Hewlett-Packard 6890 series
chromatograph equipped with a CTC Analysis Combi Pal autosampler by Leap Technologies (Carrboro, NC), a
split mode capillary injection system, a flame ionization detector, and a Supelco β-dex 120 column with helium
as the carrier gas. Analytical achiral GLC was performed on a Hewlett-Packard 6890 series chromatograph
equipped with a split mode capillary injection system, a flame ionization detector, and a Hewlett-Packard Ultra
1
capillary column (0.33 μm film thickness, 25 m length, 0.2mm ID) with helium as the carrier gas. Analytical
chiral supercritical fluid chromatography (SFC) was performed on a Berger Instruments supercritical
chromatograph equipped with an Alcott autosampler and a Knauer UV detector.
All reactions were conducted in oven or flame dried glassware under an inert atmosphere of nitrogen or
argon. Toluene, d -toluene, and d -benzene were distilled over CaH and degassed by freeze-pump-thaw cycles
8 6
2
prior to use. Anhydrous tetrahydrofuran (THF), methylene chloride, and diethyl ether were purified using a
Pure Solv MD-4 solvent purification system from Innovative Technology Inc. by passing the solvent through
two activated alumina columns after being purged with Ar. Activated enone substrates used in the conjugate
allylation were synthesized by the addition of the desired alkyl-substituted vinyl lithium to the Weinreb amide
prepared from the desired cinnamic acid derivative and is described below. Note that the activated enones used
in Table 1 and Table 3, entries 1, 3, and 4, were synthesized as previously described (Sieber, J. D.; Liu, S.;
Morken, J. P. J. Am. Chem. Soc. 2007, 129, 2214.). Bis(1,5-cyclooctadiene)nickel(0) was purchased from
Strem Chemical Company. 5-fluoro-2-methylbenzaldehyde was purchased from Oakwood Chemicals and used
without further purification. All other reagents were purchased from either Fisher or Aldrich Chemical
Companies and used directly.
Supporting Information Page S-2

Ligand Synthesis.
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
t-Bu
O
O
O
P
O
O
O
OH
OH
Me
Me
Me
Me
PhPCl , TEA
2
THF, 4Å MS
t-Bu
t-Bu
t-Bu t-Bu
t-Bu t-Bu
To a mixture of 0.898 g (0.981 mmol) of diol (synthesized from L-tartaric acid according to: Seebach,
D.; Beck, A. K.; Keckel, A. Angew. Chem. Int. Ed. 2001, 40, 92.) and 4 Å molecular sieves in 3.9 mL of THF at
o
0
C was added 0.32 ml (2.3 mmol) of triethylamine. Next, 150 μL (1.08 mmol) of dichlorophenylphosphine
was added dropwise. The reaction was allowed to warm to room temperature and stirred here for 2 h. The
reaction was diluted with Et O, filtered through celite, and concentrated under reduced pressure. Column
2
chromatography (SiO
2
, hexanes:EtOAc) afforded 0.726 g (73%) of phosphonite ligand as a white solid. mp
o
2
40-260 C (decomp.). R = 0.40 (SiO , 30:1 hexanes:EtOAc); IR (CH Cl solution): 3075 (m), 2968 (s), 2873
f
2
2
2
1 1
-
(
3
s), 1797 (w), 1595 (s), 1482 (s), 1369 (s), 1249 (s), 1205 (s), 1167 (s) cm ; H NMR (CDCl ): δ 7.96-8.30 (2H,
m), 7.67 (2H, s), 7.55 (2H, s), 7.38-7.53 (5H, m), 7.26 (2H, d, J = 6.5 Hz), 7.21 (2H, d, J = 7.5 Hz), 7.14 (2H,
s), 5.60 (1H, dd, J = 8.8 Hz, J = 3.5 Hz), 4.89 (1H, d, J = 8.8 Hz), 1.56 (3H, s) 1.20-1.33 (72H, m), 0.11 (3H, s);
1
3
C NMR (CDCl
3
): δ 149.8, 149.5, 148.9, 148.8, 146.3, 145.6, 145.5, 142.6, 142.5, 141.6, 140.6, 130.5, 130.1,
1
8
29.9, 128.2, 128.1, 123.8, 122.3, 121.6, 120.7, 120.43, 120.38, 120.2, 84.39, 84.36, 84.24, 84.18, 84.09, 83.94,
3.17, 83.13, 35.02, 34.88, 34.77, 34.75, 31.53, 31.48, 31.45, 31.41, 28.09, 23.68. P NMR (CDCl ): δ 154.3.
3
3
1
+
+
20
D
o
LRMS (ESI+) Calc’d for C69
0
H
97
O
4
P (M + Na + H) : 1044.7 Found (M + Na + H) : 1044.6. [α]
= -44 (c =
.5, CHCl3).
o
3
,5-(Me) TADDOLPPh. Prepared in 62% yield. A white solid. mp 116-130 C
2
(
sealed capillary, decomp.). R = 0.35 (SiO , 15:1 hexanes:EtOAc); IR (CH Cl
f 2 2 2
solution): 2991 (m), 2920 (s), 2865 (m), 1776 (w), 1599 (s), 1463 (s), 1379 (m),
-
1 1
1
(
252 (m), 1214 (s), 1155 (s) cm ; H NMR (CDCl
5H, s), 7.31 (2H, s), 7.12 (2H, s), 7.09 (2H, s), 6.96 (1H, s), 6.91 (2H, s), 6.86 (1H,
s), 5.59 (1H, dd, J = 8.5 Hz, J = 5.5 Hz), 4.81 (1H, d, J = 8.5 Hz), 2.35 (6H, s), 2.32
3
): δ 7.85-7.94 (2H, m), 7.54
O
O
P
O
Me
Me
O
13
(
12H, s), 2.30 (6H, s), 1.62 (3H, s) 0.26 (3H, s); C NMR (CDCl ): δ 146.7, 146.1,
3
1
1
8
41.6, 141.3, 137.1, 136.8, 136.7, 136.2, 130.3, 129.9, 129.7, 129.1, 128.9, 128.7,
28.3, 128.2, 127.2, 126.3, 125.3, 125.2, 111.2, 84.14, 83.23, 83.16, 82.79, 82.55,
3
1
2.14, 27.97, 25.08, 21.67, 21.55. P NMR (CDCl
3
): δ 155.7. LRMS (ESI+)
+
+
20
o
Calc’d for C45
H
49
O
4
P (M + Na) : 707.3 Found (M + Na) : 706.7. [α]
D
= -80 (c = 3.0, CHCl ).
3
Supporting Information Page S-3

t
t-Bu
2 5
3,5-( Bu) TADDOLPNC H10. Prepared according to: Woodward, A. R.; Burks,
t-Bu
H. E.; Chan, L. M.; Morken, J. P. Org. Lett. 2005, 7, 5505 in 82% yield. A white
o
t-Bu
solid. mp 192-200 C (sealed capillary). R = 0.33 (SiO , 30:1 hexanes:EtOAc); IR
f
2
t-Bu
(
CH
2 2
Cl solution): 3075 (w), 2966 (s), 2906 (m), 2865 (m), 1784 (w), 1599 (m),
O
P N
O
-1 1
O
O
Me
Me
1450 (m), 1358 (m), 1252 (m), 1201 (m), 1164 (m) cm ; H NMR (CDCl ): δ
3
7
(
1
.66 (4H, s), 7.44 (2H, br s), 7.27 (1H, s), 7.21-7.25 (3H, m), 7.17 (2H, s), 5.26
1H, dd, J = 6.8 Hz, J = 1.6 Hz), 4.70 (1H, d, J = 6.8 Hz), 3.32-3.49 (4H, m), 1.60-
.75 (6H, m), 1.46 (3H, s), 1.31 (18H, s), 1.30 (18H, s), 1.28 (18H, s), 1.27 (18H,
t-Bu
t-Bu
1
3
s), 0.09 (3H, s); C NMR (CDCl
1
8
3
): δ 149.5, 149.1, 148.7, 148.6, 146.5, 146.19,
46.17, 142.1, 141.2, 123.7, 122.0, 121.6, 120.5, 120.1, 120.0, 119.8, 109.7, 83.79,
3.62, 82.43, 82.35, 81.06, 45.10 (d, J = 20 Hz), 35.01, 34.94, 34.83, 31.56,
t-Bu t-Bu
2
CP
3
31
3
1.52, 28.02, 27.53 (d, JCP = 4.7 Hz), 25.50, 24.04. P NMR (CDCl
3
): δ 137.8. LRMS (ESI+) Calc’d for
+
+
20
o
C
68
H
102NO
4
P (M) : 1027.8 Found (M) : 1027.8. [α]
D
= -40 (c = 3.0, CHCl ).
3
t
t-Bu
3,5-( Bu) TADDOLPOEt. Prepared according to: Woodward, A. R.; Burks, H.
t-Bu
2
E.; Chan, L. M.; Morken, J. P. Org. Lett. 2005, 7, 5505 with EtOH as the trapping
o
t-Bu
t-Bu
reagent in 75% yield. A white solid. mp 72-100 C (sealed capillary). R = 0.36
f
t-Bu
(
SiO
2
2 2
, 30:1 hexanes:EtOAc); IR (CH Cl solution): 3075 (w), 2961 (s), 2902 (m),
O
O
O
2
1
868 (m), 1788 (w), 1599 (m), 1476 (m), 1451 (m), 1392 (m), 1358 (m), 1248 (m),
Me
Me
P OEt
O
-1 1
202 (m), 1168 (m) cm ; H NMR (CDCl ): δ 7.55 (2H, s), 7.49 (2H, s), 7.36
3
(
2H, s), 7.21-7.32 (6H, m), 5.20 (1H, d, J = 8.4 Hz), 5.07 (1H, d, J = 8.4 Hz), 4.30-
.42 (1H, m), 3.97-4.10 (1H, m), 1.18-1.36 (75H, m), 1.09 (3H, s), 0.31 (3H, s);
t-Bu
4
1
3
C NMR (CDCl ): δ 149.7, 149.2, 148.9, 148.7, 145.7, 141.3, 140.9, 123.6,
3
1
8
23.3, 123.0 121.6, 121.4, 120.7, 120.3, 120.2, 120.1, 110.9, 84.21, 83.50, 83.27,
3.13, 82.51, 58.59, 34.92, 34.87, 34.83, 31.53, 31.27, 27.18, 25.17, 22.71, 17.10,
t-Bu t-Bu
31
+
+
1
1
4.15. P NMR (CDCl
3
97 5
): δ 133.5. LRMS (ESI+) Calc’d for C65H O P (M + Na) : 1011.7 Found (M + Na) :
2
0
o
011.3. [α]
D
3
= -68 (c = 3.0, CHCl ).
Representative procedure for the synthesis of activated enone substrates.
I
O
EDCI
O
R
O
cat. DMAP
nBuLi
THF, -78 C
OMe
Ar
OH
Ar
N
o
Ar
R
ClH NMe(OMe)
2
Me
TEA, CH Cl
2
2
Amide synthesis: To 0.405 g (2.22 mmol) of trans-3-chlorocinnamic acid and 0.325 g (3.33 mmol) of
N, O-dimethylhydroxylamine hydrochloride in 9 mL of CH Cl was added 0.0542 g (0.444 mmol) of 4-
dimethylamino)pyridine (DMAP) followed by 0.638 g (3.33 mmol) of N-(3-dimethylaminopropyl)-N’-
ethylcarbodiimide hydrochloride (EDCI). This mixture was put under N and 0.44 mL (3.3 mmol) of
2
2
(
2
triethylamine was added dropwise. After addition, the mixture was stirred overnight at ambient temperature.
The final mixture was transferred to a separatory funnel, washed with water, then 1 M HCl (2x), and then
saturated NaHCO . The organic layer was dried with anhydrous Na SO and concentrated under reduced
3
2
4
pressure. Silica gel chromatography (hexanes:EtOAc) afforded 0.435 g (87%) of the Weinreb amide as a white
solid. All cinnamic acid derivatives were commercially available except for the acids required to prepare the
Supporting Information Page S-4

benzyl-protected indole substrate, the p-trifluoromethylphenyl substituted substrate, and the 5-fluoro-2-
methylphenyl substituted substrate. These Weinreb amides were prepared via Horner-Wadsworth-Emmons
olefination between diethyl(N-methoxy-N-methylcarbamoylmethyl)phosphonate and 1-benzyl-1H-indole-3-
carbaldehyde, p-trifluoromethylbenzaldehyde, or 5-fluoro-2-methylbenzaldehyde, respectively (Netz, D. F.;
Seidel, J. L. Tetrahedron Lett. 1992, 33, 1957.).
o
Vinyl lithium addition: To 0.426 g (1.90 mmol) of (E)-1-iodoheptene in 2 mL of THF at –78 C was
added 0.76 mL (1.9 mmol) of a 2.5 M solution of n-BuLi in hexane dropwise. This solution was stirred at this
temperature for 30 min and then transferred via canula to a solution of 0.215 g (0.951 mmol) of (E)-3-(3-
o
chlorophenyl)-N-methoxy-N-methylacrylamide in 10 mL of THF at –78 C. After complete addition, TLC
o
analysis showed complete consumption of the starting material after 15 min at –78 C, so the reaction was
subsequently quenched with satd. NH
M HCl and Et O. The organic layer was collected after shaking, and the aqueous layer was extracted with Et
1x). The combined organics were washed with H O, then brine, and finally dried over anhydrous Na SO , and
4
Cl(aq). The crude reaction was transferred to a separatory funnel with 1
2
2
O
(
2
2
4
concentrated using reduced pressure. Silica gel chromatography (hexanes/EtOAc) of the crude mixture
afforded 0.203 g (81%) of (1E, 4E)-1-(3-chlorophenyl)deca-1,4-dien-3-one as a light-yellow solid.
O
(E)-3-(3-chlorophenyl)-N-methoxy-N-methylacrylamide. A white solid. mp 48-52
o
OMe C. R
2 2 2
= 0.29 (SiO , 2:1 Hexanes:EtOAc); IR (CH Cl solution): 3069 (m), 2974 (m),
f
N
2
(
930 (m), 2823 (m), 1659 (s), 1615 (s), 1564 (s), 1469 (s), 1425 (s), 1389 (s), 1199 (s)
Me
-1 1
m) cm ; H NMR (CDCl
m), 7.22-7.32 (2H, m), 6.99 (1H, d, J = 16 Hz), 3.74 (3H, s), 3.27 (3H, s); C NMR
): δ 166.3, 141.7, 136.9, 134.6, 129.9, 129.6, 127.4, 126.4, 117.1, 61.91, 32.45. LRMS (ESI+) Calc’d
3
): δ 7.62 (1H, d, J = 16 Hz), 7.52 (1H, s), 7.34-7.42 (1H,
13
Cl
(
CDCl
3
+
+
for C H ClNO (M) : 225.1 Found (M) : 225.6.
1
1
12
2
O
f 2
(E)-N-methoxy-N-methyl-3-o-tolylacrylamide. A colorless oil. R = 0.35 (SiO , 1:1
OMe Hexanes:EtOAc); IR (neat): 3062 (w), 2968 (m), 2936 (m), 1659 (s), 1615 (s), 1464
N
-1 1
(
m), 1413 (m), 1388 (s), 1180 (m) cm ; H NMR (CDCl
3
): δ 7.99 (1H, d, J = 16 Hz),
Me
Me
7.57 (1H, d, J = 8.0 Hz), 7.12-7.26 (3H, m), 6.92 (1H, d, J = 16 Hz), 3.72 (3H, s), 3.28
1
3
(
3
3H, s), 2.41 (3H, s); C NMR (CDCl
3
): δ 166.8, 141.0, 137.5, 134.0, 130.5, 129.4, 126.1, 126.0, 116.8, 61.75,
+ +
2.39, 19.76. LRMS (ESI+) Calc’d for C12H15NO (M) : 205.1 Found (M) : 205.6.
2
O
(E)-N-methoxy-N-methyl-3-(2-(trifluoromethyl)phenyl)acrylamide. A colorless
OMe oil. R
= 0.15 (SiO , 3:1 Hexanes:EtOAc); IR (neat): 3075 (w), 2974 (m), 2936 (m),
823 (w), 1841 (w), 1658 (s), 1627 (s), 1488 (s), 1381 (s), 1312 (s), 1287 (s), 1161 (s),
f
2
N
2
Me
-
1 1
CF3
1123 (s) cm ; H NMR (CDCl
d, J = 8.0 Hz), 7.65 (1H, d, J = 8.0 Hz), 7.53 (1H, t, J = 8.0 Hz), 7.42 (1H, d, J = 8.0
): δ 8.06 (1H, app dq, J = 16 Hz, J = 2.4 Hz), 7.70 (1H,
3
1
3
Hz), 6.96 (1H, d, J = 16 Hz), 3.72 (3H, s), 3.28 (3H, s); C NMR (CDCl
28.7 (q, JCF = 30 Hz), 127.9, 126.0 (q, JCF = 5.5 Hz), 123.9 (q, JCF = 272 Hz), 120.3, 61.88, 32.42. LRMS
APPI) Calc’d for C12
3
): δ 165.9, 138.9, 134.3, 131.9, 129.0,
2
3
1
1
(
+
+
H
12
F
3
NO
2
(M + H) : 260.1 Found (M + H) : 260.1.
Supporting Information Page S-5

O
(E)-3-(benzo[d][1,3]diolol-5-yl)-N-methoxy-N-methylacrylamide.
A white
, 1:1 Hexanes:EtOAc); IR (CH Cl
solution): 2974 (m), 2936 (m), 2905 (m), 1841 (w), 1652 (s), 1614 (s), 1501 (s),
o
OMe solid. mp 107-110 C. R
= 0.21 (SiO
O
O
f
2
2
2
N
Me
-1 1
1
3
444 (s), 1375 (s), 1255 (s), 1180 (m) cm ; H NMR (CDCl ): δ 7.59 (1H, d, J =
1
(
6
6 Hz), 7.03 (1H, s), 6.99 (1H, d, J = 8.0 Hz), 6.81 (1H, d, J = 16 Hz), 6.75 (1H, d, J = 8 Hz), 5.94 (2H, s), 3.70
3H, s), 3.25 (3H, s); C NMR (CDCl
1.72, 32.44. LRMS (ESI+) Calc’d for C12H13NO (M) : 235.1 Found (M) : 235.6.
4
1
3
3
): δ 166.9, 149.0, 148.0, 142.9, 129.4, 124.0, 113.6, 108.3, 106.4, 101.3,
+
+
O
(E)-3-(1-benzyl-1H-indol-3-yl)-N-methoxy-N-methylacrylamide.
A white
OMe solid. mp 42-46 C. R
= 0.14 (SiO , 2:1 Hexanes:EtOAc); IR (CH Cl solution):
f 2 2 2
o
N
3
106 (m), 3055 (m), 2968 (m), 2936 (m), 1651 (s), 1608 (s), 1526 (m), 1469 (s),
Me
-1 1
N
1381 (s), 1167 (m) cm ; H NMR (CDCl
): δ 7.96 (1H, d, J = 16 Hz), 7.90-8.0
3
(
1H, m), 7.40 (1H, s), 7.20-7.34 (6H, m), 7.10 (2H, d, J = 6.4 Hz), 7.05 (1H, d, J =
1
3
1
1
6 Hz), 5.26 (2H, s), 3.79 (3H, s), 3.31 (3H, s); C NMR (CDCl ): δ 168.1,
3
37.4, 136.4, 136.2, 132.1, 128.7, 127.8, 126.7, 126.2, 122.8, 121.1, 120.4, 113.0,
+
+
1
3
10.7, 110.3, 61.59, 50.20, 32.51. LRMS (APPI) Calc’d for C20
21.2.
20 2 2
H N O (M + H) : 321.2 Found (M + H) :
Me
F
O
(E)-3-(5-fluoro-2-methylphenyl)-N-methoxy-N-methylacrylamide.
The title
OMe compound was prepared via Horner-Wadsworth-Emmons olefination with 5-fluoro-2-
N
o
methylbenzaldehyde in 78% yield. A white solid. mp 68-72 C. R = 0.14 (SiO , 3:1
f
2
Me
hexanes:EtOAc); IR (CH
(
2
Cl
s), 1589 (m), 1495 (s), 1412 (m), 1381 (s), 1262 (m), 1179 (m) cm ; H NMR
CDCl ): δ 7.88 (1H, dd, J = 16 Hz, J = 1.6 Hz), 7.23 (1H, dd, J = 9.6 Hz, J = 2.4 Hz),
2
solution): 3075 (w), 2973 (m), 2936 (m), 1658 (s), 1620
-1
1
(
3
7
.10 (1H, dd, J = 8.4 Hz, J = 5.6 Hz), 6.90 (1H, dt, J = 8.4 Hz, J = 2.4 Hz), 6.88 (1H, d, J = 16 Hz), 3.73 (3H,
s), 3.27 (3H, s), 2.35 (3H, s); C NMR (CDCl ): δ 166.4, 161.1 (d, JCF = 242 Hz), 139.9, 135.6 (d, JCF = 7.0
Hz), 133.1, 131.9 (d, J = 7.8 Hz), 117.9, 116.2 (d, J = 20 Hz), 112.4 (d, J = 22 Hz), 61.84, 32.41.
1
3
1
3
3
3
2 2
CF
CF
CF
+
+
2
LRMS (APPI) Calc’d for C12H14FNO (M + H) : 224.1 Found (M + H) : 224.1.
O
(1E, 4E)-1-phenylhepta-1,4-dien-3-one. Prepared in 90% yield from the Weinreb
amide. A yellow oil. R = 0.29 (SiO , 10:1 Hexanes:EtOAc); IR (neat): 3031 (w),
968 (m), 2936 (m), 2879 (w), 1659 (s), 1633 (s), 1602 (s), 1450 (m), 1349 (m), 1199
f
2
2
-1 1
(
m) cm ; H NMR (CDCl
3
): δ 7.63 (1H, d, J = 16 Hz), 7.56 (2H, m), 7.38 (3H, m),
7
1
1
1
.05 (1H, dt, J = 16 Hz, J = 6.4 Hz), 6.97 (1H, d, J = 16 Hz), 6.42 (1H, d, J = 16 Hz), 2.30 (2H, p, J = 7.2 Hz),
.11 (3H, t, J = 7.2 Hz) 1.10-1.40 (5H, m); C NMR (CDCl
28.23, 128.19, 124.6, 25.77, 12.30. LRMS (APPI) Calc’d for C H O (M + H) : 187.1 Found (M + H) :
1
3
3
): δ 189.4, 149.7, 143.0, 134.7, 130.2, 128.8,
+ +
1
3
14
87.1.
O
(1E, 4E)-1-(3-chlorophenyl)deca-1,4-dien-3-one. Prepared in 73% yield
o
from the Weinreb amide. An off-white solid. mp 38-40 C. R
f 2
= 0.19 (SiO ,
1
5:1 Hexanes:EtOAc); IR (CH Cl solution): 3031, (w), 2955 (s), 2924 (s),
2
2
Cl
Supporting Information Page S-6

-
1
1
2
(
(
7
854 (s), 2817 (w), 1948 (w), 1665 (s), 1602 (s), 1463 (m), 1419 (m), 1293 (m), 1199 (m) cm ; H NMR
CDCl ): δ 7.52 (1H, d, J = 16 Hz), 7.52 (1H, m), 7.39 (1H, dt, J = 6.8 Hz, J = 2.0 Hz), 7.25-7.34 (2H, m), 6.99
1H, dd, J = 16 Hz, J = 7.2 Hz), 6.94 (1H, d, J = 16 Hz), 6.74 (1H, dt, J = 16 Hz, J = 1.6 Hz), 2.25 (2H, q, J =
3
1
3
.2 Hz), 1.48 (2H, p, J = 7.2 Hz), 1.24-1.38 (4H, m) 0.871 (3H, t, J = 7.2 Hz); C NMR (CDCl
3
): δ 188.7,
1
48.8, 141.0, 136.6, 134.8, 130.03, 130.00, 129.3, 127.7, 126.5, 125.7, 32.700, 31.38, 27.81, 22.44, 13.96.
+
+
LRMS (APPI) Calc’d for C H ClO (M + H) : 263.1 Found (M + H) : 263.1.
1
6
19
O
(1E, 4E)-1-(4-methoxyphenyl)deca-1,4-dien-3-one. Prepared in 90%
yield from the Weinreb amide. A yellow oil. R = 0.11 (SiO , 10:1
f
2
Hexanes:EtOAc); IR (neat): 3006 (w), 2955 (m), 2930 (m), 2861 (m),
1659 (s), 1627 (s), 1590 (s), 1508 (s), 1420 (m), 1306 (m), 1256 (s),
O
-
1 1
1
=
=
1
168 (s) cm ; H NMR (CDCl ): δ 7.56 (1H, d, J = 16 Hz), 7.46 (2H, d, J = 8.8 Hz), 6.93 (1H, dt, J = 16 Hz, J
3
7.2 Hz), 6.84 (2H, d, J = 8.8 Hz), 6.80 (1H, d, J = 16 Hz), 6.36 (1H, d, J = 16 Hz), 3.76 (3H, s), 2.20 (2H, q, J
1
3
7.2 Hz), 1.44 (2H, p, J = 7.2 Hz), 1.20-1.36 (4H, m), 0.847 (3H, t, J = 6.8 Hz); C NMR (CDCl ): δ 188.9,
3
61.3, 147.6, 142.5, 129.8, 129.1, 127.3, 122.5, 114.2, 55.17, 32.52, 31.27, 27.78, 22.34, 13.87. LRMS (APPI)
+
+
22 2
Calc’d for C17H O (M + H) : 259.2 Found (M + H) : 259.2.
O
(1E, 4E)-1-o-tolyldeca-1,4-dien-3-one. Prepared in 89% yield from the
Weinreb amide. A yellow oil. R = 0.25 (SiO , 15:1 Hexanes:EtOAc); IR
f
2
(
neat): 3025 (w), 2955 (s), 2930 (s), 2854 (m), 1658 (s), 1627 (s), 1596 (s),
-1 1
Me
1457 (m), 1319 (m), 1099 (m) cm ; H NMR (CDCl
Hz), 7.58 (1H, d, J = 7.6 Hz), 7.10-7.30 (3H, m), 6.99 (1H, dt, J = 16 Hz, J = 7.2 Hz), 6.89 (1H, d, J = 16 Hz),
.39 (1H, dt, J = 16 Hz, J = 1.6 Hz), 2.41 (3H, s), 2.25 (2H, q, 7.2 Hz), 1.48 (2H, p, J = 7.6 Hz), 1.20-1.40 (4H,
m), 0.88 (3H, t, J = 6.8 Hz); C NMR (CDCl
25.5, 32.61, 31.31, 27.78, 22.38, 19.71, 13.90. LRMS (ESI+) Calc’d for C17
42.7.
): δ 7.92 (1H, d, J = 16
3
6
13
3
): δ 189.0, 148.2, 140.3, 137.9, 133.6, 130.6, 129.9, 129.5, 126.1,
+
+
1
2
H22O (M) : 242.2 Found (M) :
O
(1E, 4E)-1-(2-(trifluoromethyl)phenyl)deca-1,4-dien-3-one. Prepared in
9% yield from the Weinreb amide. A yellow oil. R = 0.22 (SiO , 16:1
Hexanes:EtOAc); IR (neat): 2955 (s), 2930 (s), 2867 (m), 1659 (s), 1633 (s),
7
f
2
-
1 1
CF3
1602 (s), 1489 (m), 1313 (s), 1162 (s), 1124 (s) cm ; H NMR (CDCl ): δ
3
7
.93 (1H, d, J = 16 Hz), 7.71 (1H, d, J = 8.0 Hz), 7.65 (1H, d, J = 8.0 Hz),
7
6
.53 (1H, t, J = 8.0 Hz), 7.43 (1H, t, J = 8.0 Hz), 6.98 (1H, dt, J = 16 Hz, J = 7.2 Hz), 6.86 (1H, d, J = 16 Hz),
.39 (1H, dt, J = 16 Hz, J = 1.6 Hz), 2.24 (2H, q, J = 6.8 Hz), 1.47 (2H, p, J = 7.2 Hz),1.22-1.36 (4H, m) 0.86
13
2
(
3H, t, J = 6.8 Hz); C NMR (CDCl
3
): δ 188.9, 149.2, 138.1, 133.8, 132.0, 129.4, 128.9, 128.85 (q, JCF = 30
3
1
Hz), 128.6, 127.7, 126.0 (q, J = 5.4 Hz), 123.9 (q, J = 272 Hz), 32.68, 31.31, 27.76, 22.39, 13.88. LRMS
CF
CF
+
+
(
19 3
ESI+) Calc’d for C17H F O (M) : 296.1 Found (M) : 296.7.
O
(1E, 4E)-1-(4-trifluoromethyl)phenyl)deca-1,4-dien-3-one. Prepared
in 66% yield from the Weinreb amide. A yellow oil. R = 0.23 (SiO
6:1 Hexanes:EtOAc); IR (neat): 3043 (w), 2961 (s), 2930 (s), 2861
f
2
,
1
F3C
(m), 1923 (w), 1665 (s), 1633 (s), 1469 (m), 1419 (m), 1319 (s), 1167
Supporting Information Page S-7

-
1 1
(
s), 1135 (s) cm ; H NMR (CDCl
3
): δ 7.65 (1H, d, J = 8.7 Hz), 7.63 (1H, d, J = 8.7 Hz), 7.62 (1H, d, J = 16
Hz), 7.02 (1H, d, J = 16 Hz), 7.02 (1H, dt, J = 16 Hz, J = 6.6 Hz), 6.41 (1H, d, J = 16 Hz), 2.28 (2H, q, J = 6.6
Hz), 1.50 (2H, p, J = 7.5 Hz),1.24-1.40 (4H, m) 0.89 (3H, t, J =6.6 Hz); C NMR (CDCl
40.8, 138.2, 131.6 (q, JCF = 32 Hz), 129.2, 128.3, 126.8, 125.8 (q, JCF = 3.1 Hz), 123.8 (q, JCF = 270 Hz),
19 3
2.76, 31.42, 27.85, 22.48, 13.93. LRMS (ESI+) Calc’d for C17H F O (M) : 296.1 Found (M) : 296.7.
1
3
3
): δ 188.7, 149.2,
2
3
1
1
3
+
+
O
(1E, 4E)-1-(furan-2-yl)deca-1,4-dien-3-one. Prepared in 86% yield from the
Weinreb amide. A yellow oil. R = 0.15 (SiO , 15:1 Hexanes:EtOAc); IR
f
2
(
1
neat): 3124 (w), 3037 (w), 2955 (s), 2930 (s), 2861 (m), 1658 (s), 1633 (s),
595 (s), 1482 (m), 1306 (m), 1217 (m), 1098 (m) cm ; H NMR (CDCl ): δ
3
O
-1 1
7
.44 (1H, s), 7.36 (1H, d, J = 16 Hz), 6.93 (1H, dt, J = 16 Hz, J = 6.8 Hz), 6.85 (1H, d, J = 16 Hz), 6.60 (1H, d,
J = 3.2 Hz), 6.42 (1H, m), 6.29 (1H, d, J = 16 Hz), 2.20 (2H, q, J = 6.8 Hz), 1.44 (2H, p, J = 6.8 Hz),1.17-1.36
1
3
(
1
2
4H, m), 0.85 (3H, t, J =6.8 Hz); C NMR (CDCl ): δ 188.6, 151.4, 148.0, 144.6, 129.7,128.9, 121.8, 115.4,
3
+ +
12.4, 32.60, 31.31, 27.79, 22.39, 13.90. LRMS (APPI) Calc’d for C H O (M + H) : 219.1 Found (M + H) :
14 18 2
19.1.
O
(1E, 4E)-1-(benzo[d][1,3]dioxol-5-yl)deca-1,4-dien-3-one. Prepared in
o
8
7% yield from the Weinreb amide. An off-white solid. mp = 40-44 C.
= 0.23 (SiO , 9:1 Hexanes:EtOAc); IR (CH Cl solution): 2961 (s),
930 (s), 2861 (s), 1658 (s), 1626 (s), 1589 (s), 1488 (s), 1444 (s), 1362
O
O
R
f
2
2
2
2
-1 1
(
3
m), 1255 (s), 1205 (m), 1098 (m) cm ; H NMR (CDCl ): δ 7.51 (1H, d, J = 16 Hz), 7.04 (1H, s,), 7.01 (1H,
d, J = 8.4 Hz), 6.94 (1H, dt, J = 16 Hz, J = 7.2 Hz), 6.77 (1H, d, J = 16 Hz), 6.77 (1H, d, J = 8.4 Hz), 6.36 (1H,
dt, J = 16 Hz, J = 1.6 Hz), 5.96 (2H, s), 2.22 (2H, q, J = 7.2 Hz), 1.46 (2H, p, J = 7.2 Hz), 1.20-1.37 (4H, m)
1
3
0
1
.86 (3H, t, J = 6.4 Hz); C NMR (CDCl ): δ 188.9, 149.6, 148.2, 147.9, 142.6, 129.25, 129.16, 124.8, 122.8,
3
+
20 3
08.5, 106.4, 101.5, 32.61, 31.35, 27.84, 22.41, 13.94. LRMS (APPI) Calc’d for C17H O (M + H) : 273.1
+
Found (M + H) : 273.1.
O
(1E, 4E)-1-(1-benzyl-1H-indol-3-yl)deca-1,4-dien-3-one. Prepared in
o
8
0
8% yield from the Weinreb amide. A yellow solid. mp 84-88 C. R
f
=
.21 (SiO , 5:1 Hexanes:EtOAc); IR (CH Cl solution): 3106 (m), 3037
2
2
2
N
(w), 2961 (m), 2930 (m), 2854 (m), 1658 (m), 1627 (s), 1576 (s), 1526
-1 1
(
s), 1463 (m), 1387 (s), 1350 (m), 1281 (m), 1173 (m) cm ; H NMR
(
7
CDCl ): δ 7.94-8.00 (1H, m), 7.91 (1H, d, J = 16 Hz), 7.44 (1H, s),
3
.16-7.26 (6H, m), 7.13 (2H, dd, J = 7.6 Hz, J = 2 Hz), 6.99 (1H, dt, J =
1
8
1
5
6 Hz, J = 8.0 Hz), 6.99 (1H, d, J = 16 Hz), 6.44 (1H, dt, J = 16 Hz, J = 1.6 Hz), 5.30 (2H, s), 2.26 (2H, q, J =
1
3
.0 Hz), 1.51 (2H, p, J = 7.2 Hz) 1.23-1.41 (4H, m), 0.90 (3H, t, J = 7.2 Hz); C NMR (CDCl
3
): δ 189.2,
46.7, 137.7, 136.5, 136.0, 133.1, 133.0, 129.5, 128.9, 128.0, 126.9, 126.3, 123.1, 121.5, 120.7, 113.2, 110.5,
+
0.+46, 32.65, 31.44, 27.98, 22.49, 14.01. LRMS (APPI) Calc’d for C25
H27NO (M + H) : 358.2 Found (M +
H) : 358.2.
Supporting Information Page S-8

Me
F
O
(1E, 4E)-1-(5-fluoro-2-methylphenyl)deca-1,4-dien-3-one. Prepared in
2% yield from the Weinreb amide. A yellow oil. R = 0.11 (SiO , 20:1
8
f
2
hexanes:EtOAc); IR (neat): 2955 (m), 2930 (s), 2861 (m), 1659 (s), 1627 (s),
-
1 1
1
489 (s), 1338 (m), 1237 (m) cm ; H NMR (CDCl
3
): δ 7.83 (1H, dd, J = 16
Hz, J = 1.6 Hz), 7.26 (1H, dd, J = 9.6 Hz, J = 2.4 Hz), 7.12 (1H, dd, J = 8.4
Hz, J = 5.6 Hz), 6.99 (1H, dt, J = 16 Hz, J = 6.8 Hz), 6.95 (1H, dt, J = 8.4 Hz, J = 2.4 Hz), 6.86 (1H, d, J = 16
Hz), 6.36 (1H, dt, J = 16 Hz, J = 1.6 Hz), 2.37 (3H, s), 2.26 (2H, q, J = 6.8 Hz), 1.49 (2H, p, J = 7.2 Hz), 1.21-
1
3
1
1
1
2
.37 (4H, m), 0.88 (3H, t, J = 6.8 Hz); C NMR (CDCl ): δ 188.8, 161.2 (d, J = 242 Hz), 148.8, 139.2,
3
CF
3
3
2
2
35.4 (d, JCF = 7.8 Hz), 133.6, 132.0 (d, JCF = 7.8 Hz), 129.6, 126.3, 116.7 (d, JCF = 21 Hz), 112.4 (d, JCF
=
1
9
2 Hz), 32.72, 31.38, 27.83, 22.45, 19.03, 13.96; F NMR (CDCl
C H FO (M + H) : 261.2 Found (M + H) : 261.2.
3
): δ 93.28 (m). LRMS (APPI) Calc’d for
+
+
1
7
21
Represenative procedure for the conjugate allylation catalyst survey (Table 1):
An oven-dried 2-dram vial equipped with a magnetic stir-bar was charged with 3.0 mg (0.011 mmol) of
bis(1,5-cyclooctadiene)nickel, 11.8 mg (0.0218 mmol) of chiral ligand 6, and 0.73 mL of THF in a dry-box
under an argon atmosphere. The vial was capped and stirred for 45 min. Next, 22.0 mg (0.263 mmol) of
allylboronic acid pinacol ester was added, followed by 25.0 mg (0.109 mmol) of (1E, 4E)-1-phenyldeca-1,4-
dien-3-one. The vial was capped, taped with electrical tape, removed from the dry-box, and allowed to stir at
ambient temperature for 8 h. After this time period, degassed water (N sparge) was added and the mixture
2
2 2
transferred to a separatory funnel with CH Cl . After swirling the layers, the organic layer was collected and
the aqueous layer washed with CH Cl (2x). The combined organic layers were dried with anhydrous Na SO ,
2
2
2
4
1
and volatiles were removed under reduced pressure. Analysis of the crude reaction mixture using H NMR was
used to determine the chemoselectivity of the reaction. Silica gel chromatography (hexanes/EtOAc) afforded
1
0.6 mg (36%) of the conjugate allylation product as a mixture of isomers.
Notes: Entry 1 was performed according to: Sieber, J. D.; Liu, S.; Morken, J. P. J. Am. Chem. Soc.
007, 129, 2214. Entry 2 uses 2.5 mol% Pd (dba) and 6 mol% ligand and went for 24 h reaction time.
2
2
3
Representative procedure for the asymmetric conjugate allylation (Tables 2, 3, 5):
An oven-dried 2-dram vial equipped with a magnetic stir-bar was charged with 3.0 mg (0.011 mmol) of
bis(1,5-cyclooctadiene)nickel, 22.4 mg (0.0219 mmol) of chiral ligand 14, and 0.44 mL of toluene in a dry-box
under an argon atmosphere. The vial was capped and stirred for 45 min. Next, 44.2 mg (0.263 mmol) of
allylboronic acid pinacol ester was added followed by 50.0 mg (0.219 mmol) of (1E, 4E)-1-phenyldeca-1,4-
dien-3-one. The vial was capped, taped with electrical tape, removed from the dry-box, and allowed to stir at
ambient temperature. After this time period, degassed water (N sparge) was added and the mixture transferred
2
to a separatory funnel with CH
layer washed with CH Cl (2x). The combined organic layers were dried with anhydrous Na
were removed under reduced pressure. Analysis of the crude reaction mixture using either H NMR or GLC
analysis was used to determine the chemoselectivity of the reaction. Silica gel chromatography
hexanes/EtOAc) afforded 43.7 mg (74%) of the conjugate allylation product.
2
Cl
2
. After swirling the layers, the organic layer was collected and the aqueous
2
2
2
SO , and volatiles
4
1
(
Supporting Information Page S-9

Procedure for conjugate allylation with unactivated substrates (Scheme 3):
The conjugate allylation performed on benzylidene acetone, depicted in Scheme 3, was carried out using
the same procedure as described for the asymmetric conjugate allylation in Table 2.
Conjugate allylation described in Table 4:
The conjugate allylation was performed as previously described (Sieber, J. D.; Liu, S.; Morken, J. P. J.
Am. Chem. Soc. 2007, 129, 2214). Note that for entry 4, the metal, ligand, and substrate were weighed into the
t
vial, followed by dilution with THF, and lastly addition of allylboronic acid. Mixing Ni(cod)
2
and P(O-o- Bu)
3
in THF under the previously described conditions led to a black solution which did not effect the conjugate
allylation.
Supporting Information Page S-10

(
f 2
S,E)-4-phenyltrideca-1,7-dien-6-one. An oil. R = 0.19 (SiO , 40:1
O
Hexanes:EtOAc); IR (neat): 3030 (m), 2926 (s), 1697 (s), 1667 (s), 1452 (m)
-
1 1
cm ; H NMR (CDCl
dt, J = 16 Hz, J = 7.2 Hz), 5.92 (1H, d, J = 16 Hz), 5.56 (1H, ddt, J = 17 Hz, J
10 Hz, J = 7.2 Hz), 4.82-4.94 (2H, m) 3.22 (1H, p, J = 7.2 Hz), 2.76 (1H, app dd, J = 16 Hz, J = 6.6 Hz), 2.75
1H, app dd, J = 16 Hz, J = 7.6 Hz), 2.30 (2H, t, J = 7.2 Hz), 2.06 (2H, q, J = 6.8 Hz), 1.32 (2H, p, J = 7.2 Hz),
3
): δ 7.14-7.24 (2H, m), 7.04-7.14 (3H, m), 6.65 (1H,
=
(
1
3
1
1
.10-1.28 (4H, m), 0.796 (3H, t, J = 7.2 Hz); C NMR (CDCl ): δ 199.1, 147.6, 144.2, 136.2, 130.5, 128.3,
27.5, 126.2, 116.6, 46.04, 40.99, 40.62, 32.39, 31.31, 27.74, 22.42, 13.97. LRMS (ESI+) Calc’d for C19H O
26
M) : 270.2 Found (M) : 270.7. [α] = +5.9 (c = 1.0, CHCl ).
3
+
+
20
D
o
(
3
Proof of stereochemistry. Chemoselectivity was determined using achiral GLC. Enantioselectivities were
determined by comparison with authentic racemic material prepared using either triphenylphosphine or
triphenylphosphite as the achiral ligand in the conjugate allylation reaction. Absolute stereochemistry was
determined by subjecting the conjugate allylation product to ring closing metathesis conditions using the
Hoveyda-Grubbs second generation catalyst in CH Cl to afford 5-phenyl-2-cycohexen-1-one (Sieber, J. D.;
2
2
2
0
o
Liu, S.; Morken, J. P. J. Am. Chem. Soc. 2007, 129, 2214.). The optical rotation was measured ([α]D = +40 (c
0.5, CHCl )) and compared to the known literature value (Hareau, G. P-J.; Koiwa, M.; Hikichi, S; Sato, F. J.
Am. Chem. Soc. 1999, 121, 3640).
=
3
o
Achiral GLC (Ultra 1, Hewlett-Packard, 140 C) analysis of the crude reaction mixture:
Supporting Information Page S-11

o
Chiral SFC (AD-H, Chiralpak, 150 bar, 50 C, flow = 1.0 mL/min, 2.0 % MeOH) analysis of conjugate
allylation product:
Allylation
product
Racemic
Allylation product
+ racemic
coinjection
Supporting Information Page S-12

(
S,E)-4-(3-chlorophenyl)trideca-1,7-dien-6-one. An oil. R
f
(major) = 0.18
O
(
SiO , 40:1 Hexanes:EtOAc), R (minor) = 0.24 (SiO , 40:1 Hexanes:EtOAc);
2
f
2
IR (neat): 2957 (s), 2923 (s), 2853 (m), 1673 (s), 1624 (s), 1434 (m), 1367
-
1 1
(
=
7
m) cm ; H NMR (CDCl
6.8 Hz), 5.99 (1H, d, J = 16 Hz), 5.54 (1H, ddt, J = 17 Hz, J = 10 Hz, J =
.2 Hz), 4.87-5.03 (2H, m), 3.28 (1H, p, J = 7.2 Hz) 2.82 (1H, dd, J = 16 Hz,
J = 6.0 Hz), 2.80 (1H, dd, J = 16 Hz, J = 7.6 Hz), 2.34 (2H, m), 2.14 (2H, q, J = 7.2 Hz), 1.40 (2H, p, J = 7.2
3
): δ 7.00-7.20 (4H, m), 6.74 (1H, dt, J = 16 Hz, J
Cl
1
3
Hz), 1.15-1.35 (4H, m), 0.86 (3H, t, J = 7.2 Hz); C NMR (CDCl
29.6, 127.5, 126.5, 125.9, 117.0, 45.65, 40.62, 40.48, 32.43, 31.33, 27.74, 22.43, 13.97. LRMS (ESI+) Calc’d
3
): δ 198.5, 147.9, 146.4, 135.7, 134.1, 130.4,
1
+
+
20
o
for C19
H
25ClO (M) : 304.2 Found (M) : 304.7. [α]
D
3
= +4.4 (c = 2.5, CHCl ).
Proof of stereochemistry. Chemoselectivity was determined using achiral GLC (Note: the starting material
had the same retention time as the major isomer. The reported ratios are calculated assuming 95% conversion
1
as evident by the appearance of no starting material in the crude H NMR spectrum.). Enantioselectivities were
determined by comparison with authentic racemic material prepared using either triphenylphosphine or
triphenylphosphite as the achiral ligand in the conjugate allylation reaction. Absolute stereochemistry was
determined by subjecting the conjugate allylation product to ring closing metathesis conditions using the
Hoveyda-Grubbs second generation catalyst, in CH Cl , to afford 5-(m-chlorophenyl)-2-cycohexen-1-one
2
2
(
(
Sieber, J. D.; Liu, S.; Morken, J. P. J. Am. Chem. Soc. 2007, 129, 2214.). The optical rotation was measured
2
0
o
[α]
D
3
= +32 (c = 1.0, CHCl )) and compared to the known literature value (Chen, Q.; Kuriyama, M.; Soeta,
T.; Hao, X.; Yamada, K. –I.; Tomioka, K. Org. Lett. 2005, 7, 4439).
o
Achiral GLC (Ultra 1, Hewlett-Packard, 180 C) analysis of the crude reaction mixture:
Supporting Information Page S-13

o
Chiral SFC (AD-H, Chiralpak, 150 bar, 50 C, flow = 2.0 mL/min, 3.0 % MeOH) analysis of conjugate
allylation product:
Allylation
product
Racemic Allylation product
+ racemic
coinjection
Supporting Information Page S-14

(
S,E)-4-(4-methoxyphenyl)trideca-1,7-dien-6-one. An oil. R
f
= 0.18
O
(
SiO , 17:1 pentane:Et O); IR (neat): 3074 (w), 2962 (s), 2924 (s), 2861
2
2
(
s), 2055 (w), 1879 (w), 1671 (s), 1620 (s), 1514 (s), 1464 (m), 1243 (s),
-
1 1
1
180 (s) cm ; H NMR (CDCl
8 Hz), 6.72 (1H, dt, J = 16 Hz, J = 7.2 Hz), 5.98 (1H, d, J = 16 Hz),
.63 (1H, ddt, J = 17 Hz, J = 10 Hz, J = 6.8 Hz), 4.90-5.02 (2H, m) 3.75 (3H, s), 3.24 (1H, p, J = 7.6 Hz), 2.78
2H, m), 2.34 (2H, t, J = 6.8 Hz), 2.13 (2H, q, J = 7.2 Hz), 1.39 (2H, p, J = 7.2 Hz), 1.18-1.34 (4 H, m), 0.863
3
): δ 7.08 (2H, d, J = 8 Hz), 6.79 (2H, d, J
O
=
5
(
(
4
1
3
3H, t, J = 7.2 Hz); C NMR (CDCl
3
): δ 199.3, 157.9, 147.5, 136.3, 136.2, 130.5, 128.3, 116.5, 113.7, 55.16,
6.33, 40.80, 40.28, 32.40, 31.33, 27.75, 22.42, 13.99. LRMS (ESI+) Calc’d for C20H O (M) : 300.2 Found
+
28 2
+
20
o
(
M) : 300.8. [α]
D
3
= +9.5 (c = 3.0, CHCl ).
Proof of stereochemistry. Chemoselectivity was determined using achiral GLC. Enantioselectivities were
determined by comparison with authentic racemic material prepared using either triphenylphosphine or
triphenylphosphite as the achiral ligand in the conjugate allylation reaction. Absolute stereochemistry was
determined by subjecting the conjugate allylation product to ring closing metathesis conditions using the
Hoveyda-Grubbs second generation catalyst, in CH Cl , to afford 5-(p-methoxyphenyl)-2-cycohexen-1-one
2
2
(
Sieber, J. D.; Liu, S.; Morken, J. P. J. Am. Chem. Soc. 2007, 129, 2214.). Subsequent 1,4 reduction with Pd/C
and H (Chen, Q.; Kuriyama, M.; Soeta, T.; Hao, X.; Yamada, K. –I.; Tomioka, K. Org. Lett. 2005, 7, 4439.)
2
2
D
0
o
gave the corresponding saturated cyclohexanone derivative. The optical rotation was measured ([α]
1.0, CHCl )) and compared to the known literature value (Takaya, Y.; Ogasawara, M.; Hayashi, T.
Tetrahedron Lett. 1999, 40, 6957.).
= -12 (c
=
3
o
Achiral GLC (Ultra 1, Hewlett-Packard, 190 C) analysis of the crude reaction mixture:
Supporting Information Page S-15

o
Chiral SFC (AD-H, Chiralpak, 150 bar, 50 C, flow = 1.0 mL/min, 3.0 % MeOH) analysis of conjugate
allylation product:
Allylation
product
Racemic
Allylation product+
racemic coinjection
Supporting Information Page S-16

(
S,E)-4-o-tolyltrideca-1,7-dien-6-one. An oil.
R
f
2
= 0.19 (SiO , 30:1
O
hexanes:EtOAc); IR (neat): 3069 (m), 3018 (m), 2930 (s), 2861 (s), 1829 (w),
-
1 1
1
(
671 (s), 1627 (s), 1457 (m), 1262 (m) cm ; H NMR (CDCl
4H, m), 6.73 (1H, dt, J = 16 Hz, J = 7.2 Hz), 5.99 (1H, dt, J = 16 Hz, J = 1.2
Hz), 5.63 (1H, ddt, J = 17 Hz, J = 10 Hz, J = 6.8 Hz), 4.88-5.02 (2H, m) 3.60
1H, p, J = 6.8 Hz), 2.83 (2H, d, J = 6.8 Hz), 2.35 (5H, m), 2.13 (2H, q, J = 6.8 Hz), 1.39 (2H, p, J = 7.2 Hz),
3
): δ 7.00-7.18
Me
(
13
1
.18-1.35 (4 H, m), 0.87 (3H, t, J = 6.8 Hz); C NMR (CDCl ): δ 199.2, 147.5, 142.5, 136.2, 135.9, 130.5,
30.3, 126.0, 125.9, 125.7, 116.5, 45.79, 40.44, 35.65, 32.40, 31.32, 27.76, 22.44, 19.84, 13.97. LRMS (ESI+)
3
1
+
+
20
D
o
Calc’d for C20
H
28O (M) : 284.2 Found (M) : 284.8. [α]
= +6.4 (c = 0.6, CHCl
3
).
1
Proof of stereochemistry. Chemoselectivity was determined using HNMR spectroscopy; the minor isomer
1
was not observed in the crude HNMR spectrum. Enantioselectivities were determined by comparison with
authentic racemic material prepared using either triphenylphosphine or triphenylphosphite as the achiral ligand
in the conjugate allylation reaction. Absolute stereochemistry was determined by subjecting the conjugate
allylation product to ring closing metathesis conditions using the Hoveyda-Grubbs second generation catalyst,
in CH Cl , to afford 5-(o-tolyl)-2-cycohexen-1-one (Sieber, J. D.; Liu, S.; Morken, J. P. J. Am. Chem. Soc.
2
2
2
007, 129, 2214.). Subsequent 1,4 reduction with Pd/C and H (Chen, Q.; Kuriyama, M.; Soeta, T.; Hao, X.;
2
Yamada, K. –I.; Tomioka, K. Org. Lett. 2005, 7, 4439.) gave the corresponding saturated cyclohexanone
2
0
o
derivative. The optical rotation was measured ([α]
D
4
= -37 (c = 0.8, CCl )) and compared to the known
literature value (Ek, M.; Ahlberg, P. Acta. Chem. Scand. Ser. B 1984, 38, 211.).
o
Chiral SFC (AD-H, Chiralpak, 150 bar, 50 C, flow = 1.0 mL/min, 3.0 % MeOH) analysis of conjugate
allylation product:
Allylation
product
Racemic Allylation product
+ racemic
coinjection
Supporting Information Page S-17

(
f
S,E)-4-(2-(trifluoromethyl)phenyl)trideca-1,7-dien-6-one. An oil. R =
O
0
1
.18 (SiO , 30:1 hexanes:EtOAc); IR (neat): 2961 (s), 2930 (s), 2861 (s),
2
-1
1
828 (w), 1696 (s), 1457 (m), 1312 (s), 1155 (s), 1117 (s) cm ; H NMR
): δ 7.60 (1H, d, J = 8.0 Hz), 7.48 (1H, t, J = 7.5 Hz), 7.39 (1H, d, J =
.0 Hz), 7.26 (1H, t, J = 7.5 Hz), 6.76 (1H, dt, J = 16 Hz, J = 7 Hz), 6.03 (1H,
(CDCl
3
CF3
8
d, J = 16 Hz), 5.61 (1H, ddt, J = 17 Hz, J = 10 Hz, J = 7 Hz), 4.93 (1H, d, J = 17 Hz), 4.91 (1H, d, J = 10 Hz),
3
=
.74 (1H, p, J = 7 Hz), 2.84 (1H, dd, J = 16 Hz, J = 7.5 Hz), 2.80 (1H, dd, J = 16 Hz, J = 6.0 Hz), 2.40 (2H, t, J
1
3
7.5 Hz), 2.15 (2H, q, J = 7.0 Hz), 1.40 (2H, p, J = 7.5 Hz), 1.18-1.35 (4 H, m), 0.87 (3H, t, J = 7 Hz); C
2
3
NMR (CDCl ): δ 198.3, 148.0, 143.3, 135.6, 131.8, 130.0, 128.5 (q, JCF = 29 Hz), 128.0, 126.2, 125.9 (q, JCF
=
3
1
1
9
6.1 Hz), 124.4 (q, JCF = 272 Hz), 117.0, 46.45, 40.43, 36.08, 32.38, 31.28, 27.69, 22.39, 13.90. F NMR
+
+
3 25 3
(CDCl ): δ -59.81. LRMS (ESI+) Calc’d for C20H F O (M) : 338.2 Found (M) : 338.8.
Proof of stereochemistry. Chemoselectivity was determined using achiral GLC. To determine the
enantioselectivity, the title compound was subjected to ring-closing metathesis (RCM) conditions using the
Hoveyda-Grubbs second generation catalyst, in CH Cl , to afford 5-(o-trifluoromethylphenyl)-2-cycohexen-1-
2
2
one (Sieber, J. D.; Liu, S.; Morken, J. P. J. Am. Chem. Soc. 2007, 129, 2214.). This derivative was then
analyzed by chiral GLC. Stereochemical ratios were determined in comparison with authentic racemic material
prepared using either triphenylphosphine or triphenylphosphite as the achiral ligand in the conjugate allylation
reaction followed by RCM. Absolute stereochemistry was assumed to be analogous to the configuration
determined for others.
o
Achiral GLC (Ultra 1, Hewlett-Packard, 150 C) analysis of the crude reaction mixture:
Supporting Information Page S-18

o
Chiral SFC ((R,R)-Whelk-O, Pirkle Covalent, 150 bar, 50 C, flow = 2.0 mL/min, 2.0 % MeOH) analysis of
conjugate allylation-RCM product:
Allylation-
RCM
product
Racemic
Allylation-RCM
product + racemic
coinjection
Supporting Information Page S-19

(
R
3
(
S,E)-4-(4-(trifluoromethyl)phenyl)trideca-1,7-dien-6-one. An oil.
(major) = 0.19 (SiO , 30:1 hexanes:EtOAc), R (minor) = 0.24 (SiO
0:1 hexanes:EtOAc); IR (neat): 2961 (s), 2930 (s), 2854 (m), 1702
O
f
2
f
2
,
-1 1
m), 1677 (s), 1620 (s), 1331 (s), 1167 (s), 1123 (s) cm ; H NMR
F3C
(
CDCl ): δ 7.51 (2H, d, J = 8.0 Hz), 7.29 (2H, d, J = 8.0 Hz), 6.74 (1H,
3
dt, J = 16 Hz, J = 7 Hz), 5.99 (1H, d, J = 16 Hz), 5.61 (1H, ddt, J = 17 Hz, J = 10 Hz, J = 7 Hz), 4.96 (1H, d, J
=
=
17 Hz), 4.95 (1H, d, J = 10 Hz), 3.38 (1H, p, J = 7.5 Hz), 2.86 (1H, dd, J = 17 Hz, J = 7.0 Hz), 2.83 (1H, dd, J
17 Hz, J = 7.5 Hz), 2.39 (1H, dd, J = 14 Hz, J = 7.0 Hz), 2.36 (1H, dd, J = 14 Hz, J =7.0 Hz), 2.14 (2H, q, J =
1
3
7
.0 Hz), 1.39 (2H, p, J = 7.0 Hz), 1.20-1.33 (4 H, m), 0.86 (3H, t, J = 7.0 Hz); C NMR (CDCl
3
): δ 198.5,
2
3
1
1
48.4, 148.0, 135.6, 130.4, 128.6 (q, JCF = 32 Hz), 127.9, 125.3 (q, JCF = 3.9 Hz), 124.2 (q, JCF = 271 Hz),
1
9
1
3
17.2, 45.60, 40.65, 40.39, 32.38, 31.30, 27.69, 22.36, 13.89. F NMR (CDCl ): δ -63.72. LRMS (ESI+)
+
+
25 3
Calc’d for C20H F O (M) : 338.2 Found (M) : 338.8.
Proof of stereochemistry. Chemoselectivity was determined using achiral GLC. To determine the
enantioselectivity, the title compound was subjected to ring-closing metathesis (RCM) conditions using the
Hoveyda-Grubbs second generation catalyst, in CH Cl , to afford 5-(p-trifluoromethylphenyl)-2-cycohexen-1-
2
2
one (Sieber, J. D.; Liu, S.; Morken, J. P. J. Am. Chem. Soc. 2007, 129, 2214.). This derivative was then
analyzed by chiral SFC. Stereochemical ratios were determined in comparison with authentic racemic material
prepared using either triphenylphosphine or triphenylphosphite as the achiral ligand in the conjugate allylation
2
0
reaction followed by RCM. Absolute stereochemistry was determined by comparing the optical rotation ([α]
D
o
=
+37 (c = 1.0, CHCl )) of the RCM product to the known value (Chen, Q.; Kuriyama, M.; Soeta, T.; Hao, X.;
3
Yamada, K. –I.; Tomioka, K. Org. Lett. 2005, 7, 4439).
o
Achiral GLC (Ultra 1, Hewlett-Packard, 170 C) analysis of the crude reaction mixture:
Supporting Information Page S-20

o
Chiral GLC (β-dex, Supelco, 130 C) analysis of conjugate allylation-RCM product:
Allylation- Racemic Allylation-RCM
RCM
product
product + racemic
coinjection
Supporting Information Page S-21

(
S,E)-4-(furan-2-yl)trideca-1,7-dien-6-one.
inseparable mixture of constitutional isomers.
Hexanes:EtOAc, both constitutional isomers); IR (neat): 3074 (w), 2955 (s),
An oil.
Isolated as an
O
R
f
= 0.16 (SiO
2
, 30:1
-1
1
O
2
930 (s), 2854 (m), 1671 (s), 1626 (s), 1444 (m), 1362 (m) cm ; H NMR
(
CDCl ): δ 7.47 (1H, d, J = 3.2 Hz, minor), 7.28 (1H, d, J = 16 Hz, minor), 7.27 (1H, dd, J = 2.0 Hz, J = 1.2
3
Hz, major), 6.77 (1H, dt, J = 16 Hz, J = 7.2 Hz, major), 6.64 (1H, d, J = 2.0 Hz, minor), 6.61 (1H, d, J = 16 Hz,
minor), 6.46 (1H, dd, J = 3.2 Hz, J = 2.0 Hz, minor), 6.23 (1H, dd, J = 3.2 Hz, J = 2.0 Hz, major), 6.03 (1H, dt,
J = 16 Hz, J = 1.2 Hz, major), 5.98 (1H, d, J = 3.2 Hz, major), 5.67 (1H, ddt, J = 17 Hz, J = 10 Hz, J = 7.2 Hz,
major), 4.94-5.04 (4H, m, major + minor), 3.43 (1H, p, J = 7.2 Hz, major), 2.87 (1H, dd. J = 16 Hz, J = 7.2 Hz,
major), 2.75 (1H, dd, J = 16 Hz, J = 6.8 Hz, major), 2.53 (1H, dd, J = 16 Hz, J = 6.4 Hz, minor), 2.45 (1H, dd, J
=
16 Hz, J = 5.6 Hz, minor), 2.28-2.46 (3H, m, major + minor), 1.42 (2H, p, J = 7.6 Hz, major), 1.18-1.35 (12H,
1
3
m, major + minor), 0.87 (3H, t, J = 6.8 Hz, major), 0.85 (3H, t, J = 7.2 Hz, minor); C NMR (CDCl ):
3
δ (major) 198.7, 157.1, 147.8, 140.9, 135.7, 130.4, 116.9, 109.9, 105.1, 43.06, 38.00, 34.27, 32.46, 31.34, 27.76,
+
+
2
24 2
2.45, 13.98. LRMS (ESI+) Calc’d for C17H O (M) : 260.2 Found (M) : 260.7.
Proof of stereochemistry. Chemoselectivity was determined using achiral GLC. Enantioselectivities were
determined by comparison with authentic racemic material prepared using either triphenylphosphine or
triphenylphosphite as the achiral ligand in the conjugate allylation reaction. Absolute stereochemistry was
assumed to be analogous to the configuration determined for others.
o
Achiral GLC (Ultra 1, Hewlett-Packard, 145 C) analysis of the crude reaction mixture:
Supporting Information Page S-22

o
Chiral SFC (AD-H, Chiralpak, 150 bar, 50 C, flow = 1.0 mL/min, 1.0 % MeOH) analysis of conjugate
allylation product:
Allylation
product
Racemic
Allylation product
+ racemic
coinjection
Supporting Information Page S-23

(
f
S,E)-4-(5-fluoro-2-methylphenyl)trideca-1,7-dien-6-one. An oil. R =
0
2
1
6
.18 (SiO , 30:1 hexanes:EtOAc); IR (neat): 3075 (w), 3031 (w), 2955 (s),
Me
F
O
2
924 (s), 2861 (s), 1841 (w), 1697 (s), 1665 (s), 1621 (s), 1495 (s), 1457 (m),
-1 1
237 (m) cm ; H NMR (CDCl
3
): 7.03 (1H, dd, J = 8.4 Hz, J = 6.0 Hz),
.68-6.85 (3H, m), 5.99 (1H, dt, J = 16 Hz, J = 1.6 Hz), 5.60 (1H, ddt, J = 17
Hz, J = 10 Hz, J = 6.8 Hz), 4.96 (1H, d, J = 17 Hz), 4.93 (1H, d, J = 10 Hz),
.57 (1H, p, J = 7.2 Hz), 2.82 (1H, app dd, J = 16 Hz, J = 6.4 Hz), 2.78 (1H,
app dd, J = 16 Hz, J = 7.2 Hz), 2.22-2.39 (5H, m), 2.13 (2H, q, J = 7.2 Hz), 1.40 (2H, p, J = 7.2 Hz), 1.17-1.34
3
1
3
1
3
(
6
4
4H, m), 0.86 (3H, t, J = 7.2 Hz); C NMR (CDCl ): δ 198.6, 161.4 (d, J = 241 Hz), 147.7, 144.7 (d, J =
3
CF
CF
3
2
2
.2 Hz), 135.7, 131.42, 131.36 (d, JCF = 4.7 Hz), 130.4, 116.9, 112.5 (d, JCF = 21 Hz), 112.4 (d, JCF = 21 Hz),
1
9
3
5.43, 40.29, 35.73, 32.37, 31.28, 27.70, 22.39, 19.06, 13.91; F NMR (CDCl ): δ 93.93 (m). LRMS (ESI+)
Calc’d for C20H27FO (M + Na) : 325.2 Found (M + Na) : 324.7.
+
+
Proof of stereochemistry. GLC analysis of the crude reaction mixture was used to determine the
chemoselectivity of the reaction (Note: the starting material had the same retention time as the major isomer.
The reported ratios are calculated assuming 95% conversion as evident by the appearance of no starting material
1
in the crude H NMR spectrum.). The enantioselectivity was determined by measuring the enantiomeric excess
of the cyclic enone after ring-closing metathesis (Scheme 2, eq 1) and is described below. Stereochemical
ratios were determined in comparison with authentic racemic material prepared using either triphenylphosphine
or triphenylphosphite as the achiral ligand in the conjugate allylation reaction followed by RCM.
o
Achiral GLC (Ultra 1, Hewlett-Packard, 180 C) analysis of the crude reaction mixture:
Supporting Information Page S-24

o
Chiral GLC (β-dex, Supelco, 135 C) analysis of conjugate allylation-RCM product:
Allylation-
RCM
Racemic
product
Supporting Information Page S-25

(
f
S,E)-4-(benzo[d][1,3]dioxol-5-yl)trideca-1,7-dien-6-one. An oil. R =
O
0
2
.27 (SiO , 15:1 pentane:Et O); IR (neat): 3075 (m), 2962 (s), 2930 (s),
2 2
O
O
855 (s), 1841 (w), 1671 (s), 1627 (s), 1483 (s), 1444 (s), 1350 (m), 1243
-1 1
(s) cm ; H NMR (CDCl
Hz), 5.89 (2H, s), 5.62 (1H, ddt, J = 17 Hz, J = 10 Hz, J = 7.2 Hz), 4.90-
.05 (2H, m), 3.21 (1H, p, J = 7.2 Hz), 2.76 (2H, d, J = 6.8 Hz), 2.31 (2H, m), 2.13 (2H, q, J = 7.6 Hz), 1.40
2H, p, J = 7.2 Hz), 1.16-1.36 (4H, m), 0.86 (3H, t, J = 6.8 Hz); C NMR (CDCl
45.8, 138.1, 136.2, 130.5, 120.5, 116.6, 108.1, 107.7, 100.8, 46.27, 40.84, 40.83, 32.41, 31.33, 27.76, 22.42,
3
): δ 6.55-6.80 (4H, m), 5.99 (1H, d, J = 16
5
(
1
1
13
3
): δ 199.0, 147.6, 147.5,
+
+
20
D
o
3.96. LRMS (ESI+) Calc’d for C20
H
26
O
3
(M) : 314.2 Found (M) : 314.8. [α]
3
= +11 (c = 3.0, CHCl ).
Proof of stereochemistry. Chemoselectivity was determined using achiral GLC. Enantioselectivities were
determined by comparison with authentic racemic material prepared using either triphenylphosphine or
triphenylphosphite as the achiral ligand in the conjugate allylation reaction. Absolute stereochemistry was
assumed to be analogous to the configuration determined for others.
o
Achiral GLC (Ultra 1, Hewlett-Packard, 190 C) analysis of the crude reaction mixture:
Supporting Information Page S-26

o
Chiral SFC (AD-H, Chiralpak, 150 bar, 50 C, flow = 2.0 mL/min, 3.0 % MeOH) analysis of conjugate
allylation product:
Allylation
product
Racemic Allylation product
+ racemic
coinjection
Supporting Information Page S-27

(
S,E)-4-(1-benzyl-1H-indol-3-yl)trideca-1,7-dien-6-one. An oil. R
f
=
O
0
.10 (SiO , 2:1 pentane:CH Cl ); IR (neat): 3062 (m), 2924 (s), 2848
2
2
2
-1 1
(
s), 1697 (s), 1671 (s), 1463 (s), 1350 (s) cm ; H NMR (CDCl
3
): δ 7.68
(1H, d, J = 7.5 Hz), 7.00-7.32 (8H, m), 6.91 (1H, s), 6.72 (1H, dt, J = 16
N
Hz, J = 6.8 Hz), 6.02 (1H, d, J = 16 Hz), 5.75 (1H, ddt, J = 17 Hz, J = 10
Hz, J = 7.2 Hz), 5.25 (2H, s), 5.00 (1H, d, J = 17 Hz), 4.95 (1H, d, J = 10
Hz), 3.66 (1H, p, J = 7.2 Hz), 2.97 (2H, dd, J = 16 Hz, J = 7.6 Hz), 2.93
(
1H, dd, J =16 Hz, J = 7.6 Hz), 2.56 (1H, dd, J = 14 Hz, J = 6.8 Hz),
13
2
.52 (1H, dd, J = 14 Hz, J = 6.4 Hz), 2.09 (2H, q, J = 6.8 Hz), 1.15-1.40 (6H, m), 0.87 (3H, t, J = 7.2 Hz); C
NMR (CDCl ): δ 199.8, 147.4, 137.6, 136.7, 130.5, 128.6, 127.4, 127.2, 126.5, 125.4, 121.6, 119.5, 118.9,
18.0, 116.3, 109.7, 49.84, 45.36, 39.74, 32.65, 32.38, 31.31, 27.68, 22.41, 13.97. LRMS (ESI+) Calc’d for
3
1
C
+
+
20
D
o
28
H
33NO (M) : 399.3 Found (M) : 399.8. [α]
3
= +15 (c = 3.5, CHCl ).
1
Proof of stereochemistry. Chemoselectivity was determined using H NMR spectroscopy; the minor isomer
1
was not observed in the crude H NMR spectrum. Enantioselectivities were determined by comparison with
authentic racemic material prepared using either triphenylphosphine or triphenylphosphite as the achiral ligand
in the conjugate allylation reaction. Absolute stereochemistry was assumed to be analogous to the configuration
determined for others.
o
Chiral SFC (AS-H, Chiralpak, 150 bar, 50 C, flow = 1.0 mL/min, 4.0 % MeOH) analysis of conjugate
allylation product:
Allylation
product
Racemic
Allylation product
+ racemic
coinjection
Supporting Information Page S-28

(
f 2 2
S,E)-6-phenylnona-2,8-dien-4-one. An oil. R = 0.20 (SiO , 15:1 pentane:Et O); IR
O
(
neat): 3069 (m), 3024 (m), 2911 (m), 1697 (s), 1671 (s), 1627 (s), 1495 (m), 1439 (m)
-1 1
cm ; H NMR (CDCl
1H, dq, J = 16 Hz, J = 1.6 Hz), 5.63 (1H, ddt, J = 17 Hz, J = 10 Hz, J = 6.8 Hz), 4.86-
.05 (2H, m), 3.30 (1H, p, J = 7.2 Hz), 2.83 (1H, dd, J = 16 Hz, J = 6.8 Hz), 2.81 (1H, dd, J = 16 Hz, J = 7.2
3
): δ 7.10-7.35 (5H, m), 6.76 (1H, dq, J = 16 Hz, J = 6.8 Hz), 6.03
(
5
1
3
Hz), 2.37 (2H, t, J = 7.2 Hz), 1.82 (3H, dd, J = 6.8 Hz, J = 1.6 Hz); C NMR (CDCl ): δ 198.7, 144.2, 142.4,
36.2, 132.1, 128.3, 127.5, 126.2, 116.6, 46.03, 40.85, 40.60, 18.18. LRMS (ESI+) Calc’d for C15
Na) : 237.1 Found (M + Na) : 236.7. [α]
3
1
H18O (M +
+
+
20
D
o
= +9.3 (c = 2.5, CHCl
3
).
1
Proof of stereochemistry. Chemoselectivity was determined by H NMR spectroscopy; the minor isomer was
1
not observed in the crude HNMR spectrum. Stereochemical ratios were determined in comparison with
authentic racemic material prepared using either triphenylphosphine or triphenylphosphite as the achiral ligand
in the conjugate allylation reaction. Absolute stereochemistry was determined by subjecting the conjugate
allylation product to ring closing metathesis conditions using the Hoveyda-Grubbs second generation catalyst,
in CH Cl , to afford 5-phenyl-2-cycohexen-1-one (Sieber, J. D.; Liu, S.; Morken, J. P. J. Am. Chem. Soc. 2007,
2
2
2
0
o
1
29, 2214.). The optical rotation was measured ([α]D = +37 (c = 0.5, CHCl )) and compared to the known
literature value (Hareau, G. P-J.; Koiwa, M.; Hikichi, S; Sato, F. J. Am. Chem. Soc. 1999, 121, 3640).
3
o
Chiral SFC (AD-H, Chiralpak, 150 bar, 50 C, flow = 1.0 mL/min, 2.0 % MeOH) analysis of conjugate
allylation product:
Allylation Racemic Allylation product
product
+ racemic
coinjection
Supporting Information Page S-29

(
f 2
S,E)-7-phenyldeca-3,9-dien-5-one. An oil. R = 0.22 (SiO , 20:1 Hexanes:EtOAc);
O
IR (neat): 3068 (m), 3024 (m), 2968 (s), 2924 (s), 1948 (w), 1804 (w), 1697 (s), 1627
-
1 1
(
=
s), 1451 (m) cm ; H NMR (CDCl
6.8 Hz), 5.99 (1H, d, J = 16 Hz), 5.63 (1H, ddt, J = 17 Hz, J = 10 Hz, J = 6.8 Hz),
.86-5.05 (2H, m) 3.29 (1H, p, J = 7.2 Hz), 2.84 (1H, app dd, J = 16 Hz, J = 6.8 Hz), 2.82 (1H, app dd, J = 16
3
): δ 7.12-7.32 (5H, m), 6.78 (1H, dt, J = 16 Hz, J
4
1
3
Hz, J = 7.2 Hz), 2.37 (2H, t, J = 7.2 Hz), 2.16 (2H, p, J = 7.2 Hz), 1.00 (3H, t, J = 7.2 Hz); C NMR (CDCl
3
):
δ 199.1, 148.7, 144.2, 136.2, 129.6, 128.3, 127.5, 126.3, 116.6, 46.12, 40.96, 40.63, 25.50, 12.25. LRMS
+
+
20
D
o
(
ESI+) Calc’d for C H O (M + Na) : 251.2 Found (M + Na) : 250.7. [α] = +8.8 (c = 1.0, CHCl ).
1
6
20
3
1
Proof of stereochemistry. Chemoselectivity was determined by H NMR spectroscopy; the minor isomer was
1
not observed in the crude HNMR spectrum. Stereochemical ratios were determined in comparison with
authentic racemic material prepared using either triphenylphosphine or triphenylphosphite as the achiral ligand
in the conjugate allylation reaction. Absolute stereochemistry was determined by subjecting the conjugate
allylation product to ring closing metathesis conditions using the Hoveyda-Grubbs second generation catalyst,
in CH Cl , to afford 5-phenyl-2-cycohexen-1-one (Sieber, J. D.; Liu, S.; Morken, J. P. J. Am. Chem. Soc. 2007,
2
2
2
0
o
1
29, 2214.). The optical rotation was measured ([α]D = +41 (c = 0.5, CHCl )) and compared to the known
literature value (Hareau, G. P.-J.; Koiwa, M.; Hikichi, S; Sato, F. J. Am. Chem. Soc. 1999, 121, 3640).
3
o
Chiral SFC (AD-H, Chiralpak, 150 bar, 50 C, flow = 1.0 mL/min, 1.0 % MeOH) analysis of conjugate
allylation product:
Allylation
product
Racemic
Allylation product
+ racemic
coinjection
Supporting Information Page S-30