Palladium-catalysed reactions of conjugated enyne oxiranes with organoborons: A diastereoselective method of the synthesis of 2,4,5-trienol derivatives

Article abstract of DOI:10.1016/j.tet.2018.05.030

A palladium-catalysed reaction of conjugated enyne oxiranes with organoboron reagents is described. This method allows aryl-substituted vinylallenes containing a hydroxyl group on the allylic position to be synthesized, with good diastereomeric ratios, un

Full text of DOI:10.1016/j.tet.2018.05.030

Accepted Manuscript
Palladium-catalysed reactions of conjugated enyne oxiranes with organoborons: A
diastereoselective method of the synthesis of 2,4,5-trienol derivatives
Fırat Ziyanak, Melih Kuş, Leman Alkan-Karadeniz, Levent Artok
PII:
S0040-4020(18)30549-0
10.1016/j.tet.2018.05.030
TET 29537
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 12 September 2017
Revised Date: 26 January 2018
Accepted Date: 11 May 2018
Please cite this article as: Ziyanak Fı, Kuş M, Alkan-Karadeniz L, Artok L, Palladium-catalysed reactions
of conjugated enyne oxiranes with organoborons: A diastereoselective method of the synthesis of 2,4,5-
trienol derivatives, Tetrahedron (2018), doi: 10.1016/j.tet.2018.05.030.
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ACCEPTED MANUSCRIPT
Graphical Abstract
Palladium-catalysed reactions of conjugated
enyne oxiranes with organoborons: A
diastereoselective method of the synthesis of
2,4,5-trienol derivatives
Leave this area blank for abstract info.
Fırat Ziyanak,a Melih Kuş,a Leman Alkan-Karadenizb and Levent Artoka,*
aDepartment of Chemistry, Faculty of Science, Izmir Institute of Technology, Urla, Izmir 35430, Turkey
bDepartment of Chemistry, Faculty of Science, Ege University, Bornova, Izmir 35040, Turkey.

ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Palladium-catalysed reactions of conjugated enyne oxiranes with organoborons: A
diastereoselective method of the synthesis of 2,4,5-trienol derivatives
Fırat Ziyanaka, Melih Kuş,a Leman Alkan-Karadenizb and Levent Artoka,*
aDepartment of Chemistry, Faculty of Science, Izmir Institute of Technology, Urla, Izmir 35430, Turkey. E-mail: leventartok@iyte.edu.tr
bDepartment of Chemistry, Faculty of Science, Ege University, Bornova, Izmir 35040, Turkey.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
A palladium-catalysed reaction of conjugated enyne oxiranes with organoboron reagents is
described. This method allows aryl-substituted vinylallenes containing a hydroxyl group on the
allylic position to be synthesised, with good diastereomeric ratios, under mild conditions.
2009 Elsevier Ltd. All rights reserved
.
Available online
Keywords:
Allene
Vinylallene
2,4,5-trienol
Enyne oxirane
Organoboron
1. Introduction
Our group has recently developed general palladium-catalysed
methods to synthesise functionalized tetra-substituted allenes in a
series of studies of conjugated enyne compounds.5 This work was
initiated with studies of enynes containing a carbonate-leaving
group on the allylic carbon. These enynes react with CO/ROH
combinations or organoboron reagents to afford esters and aryl-
or alkenyl-substituted vinylallenes, respectively (Scheme 1).5a-c
Allenes are highly versatile reagents, with broad utility as
building blocks to a diverse array of high-value products.1 In
addition, there are quite a number of biologically active natural
products and pharmaceutical agents that contain an allene
moiety.1a,b Therefore it is of interest to develop mild and selective
methods to synthesise allenes with diverse substitution patterns2,3
that can be elaborated into specific targets.1c,4
We then extended the alkoxycarbonylation to conjugated
enynes carrying an oxirane moiety to synthesize functionalized
vinylallenes, thereby allowing the formation of 7-hydroxy-2,3,5-
trienoates stereoselectively (Scheme 1).5d,6
We demonstrate in this study that enyne oxiranes are
compliant reagents for Miyaura-Suzuki-type reactions7 and thus
produce aryl- or alkenyl-substituted vinylallenes bearing a
hydroxyl group on the allylic position (Scheme 2).
Scheme 2. This study: Palladium-catalysed arylation of enyne
oxiranes.
2. Results and discussion
Scheme 1. Palladium-catalysed alkoxycarbonylation and
Miyaura-Suzuki type reactions of enyne carbonates and enyne
oxiranes.5
A promising result was obtained in the reaction of the enyne
oxirane 1a, which had a dimethyl group on the oxirane terminus,
with phenylboronic acid in the presence of Pd(PPh3)4 (3 mol%) in

2
Tetrahedron
a THF/water (2:1) mixture at 50 °C. This reaction resulted in
Table 1. Effect of Organoboron type and other reaction
ACCEPTED MANUSCRIPT
complete conversion in 1.5 h and furnished the phenyl-
substituted vinylallene 3aa, which had a hydroxyl group on the
allylic position (Scheme 3).
parameters.a
Me
H
Me
Me
Pd(PPh3
(3 mol% Pd)
)
4
Bu
O
H
•
OH
OMe
+
Organoboron
Ph
+
Based on this promising result, the optimisation studies with
the enyne oxirane 1b, which had a disubstituted oxirane ring,
were carried out so that the stereoselectivity of the process could
be evaluated with respect to the relative configurations of the
axially-chiral allenyl moiety and the hydroxyl-substituted
chirality centre (Scheme 4). However, interestingly, the reaction
of this substrate with phenylboronic acid under the
aforementioned conditions led only to a condensation product.
Other organoboron reagents, such as PhBF3K and (PhBO)3 also
shared the same fate.
THF/water
1.5-4.0 h
H
Ph
OMe
3ba
Bu
4ba
Bu
1b
HO
OMe
Entry
Organo-
boron
THF/water Temp.
Yield
(%)b
dr of
(mL)
(°C)
3bab
3ba:4ba
1
NaBPh4
NaBPh4
NaBPh4
PhNeop
PhNeop
2:1
50
50
25
25
25
67:-
79:11
83:17
N.D.
2
2:0.5
2:0.5
2:0.5
2:0.5
75:-
3
31:33
77:-
4
73:27
76:24
5c
81:-
Me
Pd(PPh3)4
(3 mol%)
Bu
Me
Bu
aReagents and conditions: 1b (0.1 mmol), organoboron (0.3 mmol).
bDetermined by 1H NMR using p-anisaldehyde as the internal standard.
•
+
PhB(OH)2
Ph
Me
Me
THF/H2O
(2.0/1.0 mL)
50 °C
0.3 mmol
O
1a
0.1 mmol
3aa
Me
Me
HO
73% yield
cPerformed using Pd2(dba)3-CHCl3/PPh3 (3 mol% Pd, P/Pd
combination.
= 4.5:1)
1.5 h
Scheme 3. Palladium-catalysed reaction of 1a and phenylboronic
acid.
Table 2. Optimization studies.a
Entry Ligandb
Base (eq)
Time (h) Yield
(%)c
drc
Scheme 4. Palladium-catalysed reaction of 1b and organoborons.
1
TFP
–
15
23
20
30
72
40
1.5
3.5
5
65
70
66
81
70
48
92
96
90
90
92d
89
85:15
85:15
82:18
84:16
82:18
83:17
80:20
87:12
89:11
90:10
91:9
Palladium-catalysed condensation of allylic oxiranes with
organoboronic acids has been previously documented,8 so the
latter two reagents were probably also partially hydrolysed to
phenylboronic acid under aqueous conditions. Encouragingly, the
desired vinylallene product 3ba could be obtained with a
moderate yield (67%) and diastereomeric ratio (dr) of 79:21, as
2
PPh2Me
AsPh3
–
3
–
4
dppe
–
5
dppp
–
1
determined by H NMR, with the use of the NaBPh4 reagent
6
dppb
–
(Table 1, entry 1). Increasing the THF/water ratio improved the
reaction efficiency and dr to some extent (entry 2). However,
lowering the reaction temperature to 25 °C resulted in a
significant reduction in the yield and led to the formation of the
allylic substitution product 4ba (entry 3). The neopentyl glycol
ester of phenylboronic acid (2a) was also compatible—when
reacting with 1b at 25 °C in the presence of Pd(PPh3)4 or
Pd2(dba)3-CHCl3/PPh3 (3 mol% Pd; P/Pd = 4.5:1) catalyst
systems, neither the condensation by-product formation nor 4ba
were observed to form and, thus, 3ba could be obtained with a
good yield, but with a non-satisfactory dr (entries 4 and 5).
7
DPEPhos
DPEPhos
DPEPhos
DPEPhos
DPEPhos
DPEPhos
–
8
NaHCO3 (2)
Et3N (2)
9
10
11
12
(i
(i
(i
-Pr)2EtN (2)
-Pr)2EtN (4)
-Pr)2EtN (6)
2
4
6
92:8
aReagents and conditions: 1b (0.1 mmol), 2a (0.3 mmol) at 25
°C.
bP (or As)/Pd: 4.5:1; TFP: tri(2-furyl)phosphine; dppe: 1,2-Bis(di-
phenylphosphino)-ethane; dppp: 1,3-Bis(diphenylphosphino)propane;
dppb: 1,4-Bis-(diphenylphosphino)butane; DPEPhos: Bis[(2-diphe-
nylphosphino)-phenyl] ether.
Several mono and bidentate ligands were surveyed in an
attempt to improve the efficacy and stereoselectivity for the
reaction of 1b and 2a (see the supporting file), among which the
most promising ligands that provided dr levels greater than 80:20
are listed in Table 2.
cDetermined by 1H NMR using
p-anisaldehyde as the internal standard.
dYield of isolated product is provided.
The reactions in the presence of TFP, PPh2Me, AsPh3, dppe,
dppp, and dppb ligands were either unaffordably slow or had
unsatisfactory yields (entries 1–6). The best performance in terms
of the 3ba yield and reaction rate was achieved by the use of
DPEPhos ligand, albeit with somewhat lessened stereoselectivity
(entry 7).
determined to be the most suitable base and even better
diastereoselectivities were achieved by using larger amounts of
the base (entries 11 and 12).
Having completed the optimization study, we surveyed the
scope of the method against an array of neopentyl glycol esters of
arylboronic acids with a variety of substitution patterns under the
conditions of entry 11 of Table 2, which was judged to be
sufficient for the selective formation of the desired product 3.
The palladium-catalysed reaction of 1b and organoboron reagents
(2b-e) substituted with an electron donating group gave the
Gratifyingly, the presence of a base additive has been found to
be beneficial for the level of stereoselectivity (see the supporting
file) and the organic bases usually performed better than
inorganic bases (entries 8–10). The additive (i-Pr)2EtN was

expected vinylallenes in good yields and stereoselectivities in
forms effectively, the protection of the hydroxyl functionality
was not compulsory, although there was some reduction in yield
without such protection (entries 3-5). The presence of a larger
group in R3, such as 2-methoxypropan-2-yl group (1g), was also
well-tolerated by the method (entry 6). However, the reaction
was dramatically decelerated when there was only one methyl
group at the oxirane terminus (1h) (entry 7).
ACCEPTED MANUSCRIPT
relatively short reaction periods, regardless of the substitution
pattern of 2 (Table 3, entries 1-4). However, the allylic
substitution product 4bf was the main product of the reaction
carried out with the highly encumbered 2,6-dimethyl substituted
organoboron 2f, and therefore, yielded the desired 3bf in low
yield (entry 5).
Both electron-poor organoboron reagents (entries 6–8) and
naphthylborons (entries 9 and 10) were competent reagents in
terms of process efficiency and stereoselective formation of
respective products. The reactions proceeded slower when the
former organoboron reagents were used. The method was less
stereoselective for alkenylboron reagents, whereas the
structurally interesting divinylallene product 3bl could be
isolated with a synthetically useful dr (83:17) when using (E)-1-
pentenylboronic ester (entry 11). On the other hand, the reaction
with (E)-styrylboronic ester proceeded with remarkably low
diastereomeric selectivity (entry 12). Interestingly, a β-hydride
elimination product was the sole product of the reaction
performed in the presence of 3-thienylboron (2n) (entry 13).
The reactions proceeded smoothly with enyne oxiranes
bearing a terminal alkyne moiety (1i) and those bearing methyl
(1j), phenyl (1k), or ester (1l) groups on the alkynyl terminus
(R1) (entries 8–11). However, the regioselectivity of the method
was sensitive to the size of the R1 and R2 group on the alkenyl
carbon that was in the vicinity of the alkynyl moiety (entries 12–
17). When either group was larger than Bu, the formation of the
desired vinylallene products was accompanied by the
corresponding allylic substitution products 4, with varying yields
of 9–16% for enynes where R1 was Cy (1m) or t-Bu (1n) or R2
was Cy (1q) under the standard conditions. However, the
formation of these by-products could be minimized by using
Ph3P, albeit with a decrease of dr of the product. On the other
hand, the formation of 4ra was almost exclusive when R2 was t-
Bu and the DPEphos ligand was used, and 3ra formation was not
satisfactory even using the Ph3P ligand (entry 17).
The diastereomeric forms of the products 3 were estimated by
comparison with NMR spectra of 3la (entry 11) and its
diastereomeric form 3la’ synthesized in another study5d (see the
supporting information).
The enyne oxirane component of the reaction was also varied,
usually with similar success (Table 4). The substrate 1a showed a
better performance under the optimized conditions. Hence, 3aa
could be obtained in high yield (entry 1). The method was also
suitable to the synthesis of the vinylallene with a primary allylic
alcohol portion (3ca), although it was obtained in a relatively
lower yield (entry 2). While the pendant oxygen functionality
within R3 group could also be used in benzyl- or silyl-protected
Me
•
OMe
MeO2C
OH
3la'
Ph
The scope of the method was also evaluated for an enyne
oxirane with an ( )-configured alkenyl moiety (( )-1b); the
Table 3. The reaction of 1b with various organoboronic
E
E
esters.a
reaction of this reagent with 2a proceeded with low
stereoselectivity and produced 3ba′, the diastereomer of
3ba, with a 76:24 dr (Scheme 5).
Entry
1
R
Time (h) Yield (%)
drb
p-MeC6H4 2b
1.5
2
93 3bb
72 3bc
87 3bd
95 3be
28 3bf
81 3bg
78 3bh
83 3bi
92:8
90:10
92:8
91:9
74:26
92:8
90:10
92:8
91:9
91:9
83:17
70:30
–
2
m
-MeC6H4 2c
3
o-MeC6H4 2d
1.5
1.5
20
12
9
Scheme 5. The reaction of (E)-1b and 2a.
4
p-OMeC6H4 2e
5c
2,6
-CF3C6H4 2g
-ClC6H4 2h
-FC6H4 2i
-Me2C6H4 2f
6
p
7
m
8
o
6
9
1-Naphthyl 2j
2-Naphthyl 2k
1.5
2
93 3bj
88 3bk
63 3bl
10
11
12
13d
(E
)-1-Pentenyl 2l
)-Styryl 2m
4
(E
6
73 3bm
trace 3bn
3-Thienyl 2n
3
aReagents and conditions: 1b (0.1 mmol), 2 (0.3 mmol) at 25 °C.
bDetermined by 1H NMR.
cThe reaction also yielded 43% of 4bf.
Scheme 6. Palladium-catalysed reaction of 1s and 2a.
dA β-hydride elimination product was the only product of this reaction.

4
Tetrahedron
ACCEPTED MANUSCRIPT
Table 4. Arylation of enyne oxiranes.a
R2
R2
R2
R1
Pd2(dba)3-CHCl3, (3 mol% Pd)
Ligand, (P/Pd = 4.5:1)
(i-Pr)2NEt
•
R4
R3
HO
O
R4
+
Ar
ArBneop
+
R4
R3
R3
Ar
4
H
2
3
THF/water (2:0.5 mL)
R1
R1
HO
1
Entry
1
Product
Time (h)
1.5
Yield
(%)
3
drb
-
Entry
12
Product
Time (h)
8 (5)c
Yield
(%)
3
drb
91
71 (73)c
92:8
Me
•
Cy
Ph
(85:15)c
3ma
HO
MeO
OMe
+
Me
2
3
2
78
78
-
9 (trace) c
68 (71)c
N.D.
Ph
OH
Cy
4ma
1.5
91:9
13
16 (10)c
92:8
Me
Me
Bu
(88:12)c
t-Bu
•
•
Ph
Ph
3da
3na
HO
OH
HO
MeO
OMe
+
4
2.5
88
90:10
11 (5)c
N.D.
Me
Me
Bu
•
Ph
Ph
OH
3ea
t-Bu
4na
HO
OBn
Bu
Ph
5
6
2
87
87
92:8
92:8
14
15
4
67
88
89:11
92:8
Me
•
Bu
•
Ph
3oa
3fa
HO
OMe
HO
OTBDMS
Bu
2
1.5
Me
Bu
Ph
Bu
•
•
Ph
Me
3pa
3ga
Me
HO
OTBDMS
HO
OMe
3 (2)c
68 (72)c
88:12
Cy
Me
7
8
16
1
73
74
91:9
91:9
16
Bu
Ph
Bu
(85:15)c
•
•
Ph
3ha
3qa
Me
HO
HO
OMe
+
Cy
MeO
Me
16 (trace)c
N.D.
•
Ph
Ph
4qa
OH
Bu
3ia
HO
OMe
OMe
9
1
93
92:8
17
Bu
8 (3)c
Trace (16)c
62 (61)c
N.D.
t-Bu
Me
Me
•
(85:15)c
•
Ph
Ph
3ja
3ra
HO
HO
OMe
+
83:17
(81:19)c
t-Bu
MeO
10
11
3
2
93
89
91:9
Me
Ph
•
C6H4Mep-O
Ph
4ra
OH
Bu
3ke
HO
OMe
89:11
Me
MeO2C
•
Ph
3la
HO
OMe
aReagents and conditions: 1 (0.1 mmol), 2 (0.3 mmol), and DPEPhos ligand at 25 °C. The oxirane ring is in the form of E-configuration where it is applicable.
bDetermined by 1H NMR.
cPh3P ligand was used in these reactions.

days had no influence on its original diastereomeric ratio of
Finally the method was also examined for sAubCstrCateE1Ps,TwEhiDch MANUSCRIPT
had an endocyclic double bond. However, unlike its acyclic
counterparts listed herein, its reaction with 2a under the standard
conditions resulted in only a mixture of 3,5-dienone structure
(5sa) and the typical allyl-substituted by-product 4sa; therefore
the expected product of vinylallene 3sa could not be isolated
(Scheme 6). This vinylallene 3sa would have been precursor to
5sa, and after it was formed, it would have undergone successive
isomerisation and tautomarization steps to form 5sa products.
91:9.3b,5c
Evidently, the vinylallene structures of this study are well-
suited to Diels-Alder reactions, as the reaction of 3ba (dr = 91:9)
with N-phenylmaleimide proceeded with virtually complete
facial- and endo-selectivity to furnish a structurally interesting
adduct 6ba in two diastereomeric forms (91:9) (Scheme 9). The
structure of the major diastereomeric form was elucidated by
NOE studies.
It has been shown in previous studies that vinylallenes
can be converted to conjugated trienes via thermally induced
[1,5] -sigmatropic hydrogen shift.9
A hydrogen shift in this way requires that the alkenyl
moiety of 3sa be present in the (Z)-configuration, but we do
not know its exact configuration in fact. Whereas, in an our
previous study, the palladium-catalysed alkoxycarbonylation
of 1s had yielded the corresponding ester functionalized
vinylallene with exclusively (E)-configuration and no traces
of a triene product could be detected in that study (Scheme
7).5d
Scheme 8. Proposed mechanism.
Scheme 7. Pd-catalysed alkoxycarbonylation of 1s.5d
Considering that similar mechanisms are proposed for
both alkoxycarbonylation5d and arylation (this study,
Scheme 8) reactions, we cannot envisage any possibility that
could lead to the formation of 3sa in (Z) configuration.
Presumably both the locked s-cis conformational structure of
3sa and the apparent π-conjugated nature of the trienol
intermediate may have favored an isomerization process.
As for the reaction mechanism, as suggested in our previous
reports5 the catalytic cycle could begin with the formation of a π-
allylpalladium intermediate in anti-form (A), which has the R3
group oriented syn with respect to the middle allylic C−H so that
vinylallene products can ultimately form in (E)-configuration
(Scheme 8). Then, this allyl-ligated palladium species A and
organoboron 2 should undergo transmetalation to form the
intermediate B.10 The subsequent migration of the palladium unit
over the intermediate B to the distal alkynyl carbon mainly by
retention of the configuration, affords a σ-allenylpalladium
complex (C)11 and the final reductive elimination step then
completes the cycle, resulting in the target product 3. In cases
where B has R1 or R2 groups relatively large in size or increased
crowding around the palladium core metal, such a palladium shift
would be less favourable and, therefore, B would preferentially
undergo reductive elimination to furnish the by-product 4.
Scheme 9. The Diels-Alder reaction of the vinylallene 3ba with
N-phenylmaleimide.
3. Conclusion
We have demonstrated that the palladium-catalysed reactions
of enyne oxiranes and organoboronic esters can be carried out
with good stereoselectivity under mild conditions, yielding 2,4,5-
trienol derivatives. One product served as a substrate for a Diels-
Alder reaction with high stereospecificity and stereoselectivity.
4. Experimental section
4.1. General
The synthesis procedure of the starting enyne oxirane
compound 1c13 and others5d can be found elsewhere. The solvents
were dried and purified following standard procedures. All of the
reaction products were isolated by silica-gel column
chromatography and analysed by GC−MS, NMR, FTIR, and
HRMS techniques. NMR (400 MHz) spectra were recorded in
CDCl3 or C6D6. With C6D6 solvent, the 1H NMR signals of
diastereomers were usually resolved adequately, allowing
The loss of stereochemical integrity of the resulting products
probably took place during the course of the reaction cycle,
because it was observed that the vinylallene 3ba was
configurationally stable under the reaction conditions;12
subjecting the purified 3ba again to the standard conditions for 3

6
Tetrahedron
determination of diastereomeric ratios (dr) smoothly. In
129(45), 115(52), 91(100), 77(88), 56(84); HRMS (ESI)
ACCEPTED MANUSCRIPT
C19H27O2 [M+H]+: 287.2006 (calculated); 287.2008 (found).
contrast, when using CDCl3 solvent, diastereomeric signals were
all overlapped. The coupling constants of olefinic protons and
NOE studies confirmed (E)-configured structures for 3. Infrared
spectra were obtained by the ATR method with neat samples.
High-resolution mass spectral analyses of new compounds were
performed using ESI-LTQ Orbitrap and an ESI-Q-TOF mass
spectrometers.
4.3.3. (2S,6R,E)-1-methoxy-5-methyl-7-
phenylundeca-3,5,6-trien-2-ol (3ba’)
1
Isolated as a 76:24 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.45-7.41 (m, 2H), 7.20-7.15 (m, 2H), 7.08-7.04
(m, 1H), 6.55 (dd, J = 15.8, 1.4 Hz, 1H), 5.633 (dd, J = 15.8, 6.0
Hz, 1H), 4.35-4.30 (m, 1H), 3.14 (dd, A of ABX, JAB = 9.4 Hz,
JAX = 3.4 Hz, 1H), 3.11 (dd, B of ABX, JAB = 9.4 Hz, JBX = 7.9
Hz, 1H), 3.01 (s, 3H), 2.40 (t, J = 7.2 Hz, 2H), 1.86 (s, 3H), 1.57-
1.48 (m, 2H), 1.38-1.28 (m, 2H), 0.86 (t, J = 7.6 Hz, 3H); 13C
NMR (101 MHz, C6D6) δ: 208.8, 138.0, 130.5, 129.06, 127.3,
127.1, 106.3, 103.4, 77.5, 71.7, 58.9, 30.81, 30.75, 23.2, 15.9,
14.5; FTIR (νmax/cm-1): 3428, 2931, 2163, 1925, 1438, 1115, 973,
761, 692; MS (EI, m/z): 286(<5, M+) 241(20), 223(25), 199(30),
181(45), 169(100), 91(70), 77(20), 45(50).
4.2. General method for the synthesis of neopentyl borates (2)
The dry THF (1 mL) solution of organoboronic acid (10
mmol), 2,2-dimethylpropan-1,3-diol (11 mmol, 1.2 g), and
MgSO4 (14 mmol, 1.7 g) mixture was stirred overnight at room
temperature under Ar. The crude mixture was concentrated under
a reduced pressure and neopentyl borate ester derivative (2) was
purified on a silica gel column with yields varying in the range of
76-97% (hexane/ethyl acetate as the eluent).
4.3. General procedures for catalytic reactions
4.3.4. (Z)-1-methoxy-5-methyl-3-phenylundec-4-en-
6-yn-2-ol (4ba)
A palladium complex, ligand, and the dry THF (half of the
volume necessary for the reaction) were added successively into
a Schlenk apparatus that is attached to an Ar line and stirred 15
minutes at 25 °C. Then, the dry THF (remaining half volume)
solution of organoboron, enyne oxirane (1), and degassed water
were added successively. The mixture was stirred magnetically in
a preheated water or an oil bath. When the reaction was
complete, as judged by TLC analysis, the solvent was evaporated
under reduced atmosphere and the residue was purified by
column chromatography on silica gel (hexane/ethyl acetate),
affording the product 3 as colourless oil unless otherwise
mentioned. In the case of optimization studies, the reaction
mixture was filtered through a short silica gel column, washed
with Et2O, dried with MgSO4 and evaporated under reduced
1H NMR (400 MHz, CDCl3): δ 7.34-7.24 (m, 5H), 5.75 (d, J =
10.2 Hz, 1H), 4.09 (t, J = 8.4 Hz, 1H), 3.95 (t, J = 9.6 Hz, 1H),
3.54 (dd, J = 9.8, 2.7 Hz, 1H), 3.39-3.30 (m, 4H), 2.38 (t, J = 7.2
Hz, 2H), 1.82 (d, J = 1.2 Hz, 3H), 1.55-1.44 (m, 4H), 0.95 (t, J =
7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 141.0, 134.7, 128.7,
128.3, 126.7, 120.2, 94.9, 79.5, 75.2, 73.0, 59.1, 50.5, 30.9, 23.7,
22.0, 19.2, 13.6.
4.3.5. (2S,6S,E)-1-methoxy-5-methyl-7-(p-
tolyl)undeca-3,5,6-trien-2-ol (3bb)
1
Isolated as a 92:8 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.41 (d, J = 8.2 Hz, 2H), 7.05 (d, J =7.8 Hz, 2H),
6.56 (dd, J = 15.8, 1.0 Hz, 1H), 5.63 (dd, J = 15.8, 6.1 Hz, 1H),
4.34-4.28 (m, 1H), 3.14 (dd, A of ABX, JAB = 9.4 Hz, JAX = 8.2
Hz, 1H), 3.10 (dd, B of ABX, JAB = 9.4 Hz, JBX = 3.5 Hz, 1H),
3.00 (s, 3H), 2.43 (t, J = 8 Hz, 2H), 2.14 (s, 3H), 1.87 (s, 3H),
1.54 (quint, J =7.2 Hz, 2H), 1.37-1.30 (m, 2H), 0.86 (t, J = 7.6
Hz, 3H); 13C NMR (101 MHz, C6D6) δ: 208.6, 136.8, 135.1,
130.7, 129.8, 128.3, 127.1, 106.2, 103.3, 77.5, 71.7, 58.9, 30.9,
30.6, 23.2, 21.4, 16.0, 14.5; FTIR (νmax/cm-1): 3444, 2923, 1523,
1441, 1197, 1123, 961, 831, 603; MS (EI, m/z): 300(15, M+),
282(5), 225(30), 193(30), 155(50), 141(30), 105(20), 91(15),
44(100); HRMS (ESI): C20H28O2Na [M+Na]+: 323.1982
(calculated), 323.1983 (found).
1
atmosphere. The residue was analysed by H NMR using p-
anisaldehyde as the internal standard. Aldehyde and methoxy
hydrogen signals were used in the quantitative analyses.
4.3.1. (E)-2,5-dimethyl-7-phenylundeca-3,5,6-trien-
2-ol (3aa)
1H NMR (400 MHz, CDCl3) δ: 7.37-7.34 (m, 2H), 7.33-7.38
(m, 2H), 7.17-7.21 (m, 1H), 6.23 (d, J =15.9 Hz, 1H), 5.76 (d, J =
15.9 Hz, 1H), 2.45 (t, J =8.0 Hz, 2H), 1.91 (s, 3H), 1.54-1.39 (m,
4H), 1.38 (S, 6H), 0.92 (t, J =8.0 Hz, 3H); 13C NMR (100 MHz,
CDCl3) δ: 208.1, 137.4, 136.3, 128.5, 126.7, 126.3, 125.5, 105.3,
102.5, 71.2, 30.2, 30.1, 30.0, 22.6, 15.6, 14.2; FTIR (νmax/cm-1):
3356, 2923, 1609, 1362, 1142, 974, 763, 692; MS (EI, m/z):
270(<5, M+), 252(6), 195(10), 165(12), 153(15), 141(40),
128(23), 115(35), 91(62), 77(50), 59(100); HRMS (ESI), C19H25
[(M-H2O)+H]+: 253.1951 (calculated), 253.1952 (found).
4.3.6. (2S,6S,E)-1-methoxy-5-methyl-7-(m-
tolyl)undeca-3,5,6-trien-2-ol (3bc)
1
Isolated as a 90:10 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.36 (s, 1H), 7.31 (d, J = 7.8 Hz, 1H), 7.17-7.13
(m, 1H), 6.92 (dt, J = 7.4, 0.8 Hz, 1H), 6.58 (dd, J = 15.9, 1.4 Hz,
1H), 5.63 (dd, J = 15.9, 5.6 Hz, 1H), 4.34-4.30 (m, 1H), 3.13 (dd,
A of ABX, JAB = 9.4 Hz, JAX = 7.8 Hz, 1H), 3.10 (dd, B of ABX,
JAB = 9.4 Hz, JBX = 3.6 Hz, 1H), 3.00 (s, 3H), 2.44 (t, J = 6.4 Hz,
2H), 2.27 (bs, 1H), 2.14 (s, 3H), 1.88 (s, 3H), 1.59-1.51 (m, 2H),
1.40-1.30 (m, 2H), 0.86 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz,
C6D6) δ: 208.8, 138.4, 138.0, 130.6, 129.1, 128.5, 128.2, 127.8,
124.3, 106.4, 103.2, 77.5, 71.7, 58.9, 30.9, 30.8, 23.2, 21.9, 16.0,
14.5; FTIR (νmax/cm-1): 3435, 2922, 1606, 1470, 1258, 1107, 956,
797, 699; MS (EI, m/z): 300(5, M+), 237(15), 195(40), 183(85),
143(45), 105(100), 91(40), 77(25), 45(40); HRMS (ESI)
C20H29O2 [M+H]+: 301.2162 (calculated), 301.2164 (found).
4.3.2. ((2S,6S,E)-1-methoxy-5-methyl-7-
phenylundeca-3,5,6-trien-2-ol (3ba)
Isolated as a 91:9 mixture of diastereomers; white crystal;
1
m.p. 46.4-47.8 °C; H NMR (400 MHz, C6D6) δ: 7.43 (dd, J =
8.8, 1.6 Hz, 2H), 7.18 (t, J = 7.2 Hz, 2H), 7.06 (t, J = 8.0 Hz,
1H), 6.55 (dd, J = 15.8, 1.6 Hz, 1H), 5.63 (dd, J = 15.8, 5.9 Hz,
1H), 4.35-4.31 (m, 1H), 3.14 (dd, A of ABX, JAB = 9.6 Hz, JAX
=
3.8 Hz, 1H), 3.11 (dd, B of ABX, JAB = 9.6 Hz, JBX = 8.3 Hz,
1H), 3.01 (s, 3H), 2.40 (t, J = 7.2 Hz, 2H), 1.86 (s, 3H), 1.55-1.48
(m, 2H), 1.37-1.28 (m, 2H), 0.85 (t, J = 7.6 Hz, 3H); 13C NMR
(100 MHz, C6D6) δ: 208.8, 138.0, 130.4, 129.1, 128.6, 127.3,
127.1, 106.3, 103.4, 77.5, 71.7, 59.0, 30.8, 30.7, 23.1, 15.9, 14.5;
FTIR (νmax/cm-1): 3426, 2938, 1923, 1455, 1198, 1126, 968, 770,
697; MS (EI, m/z): 286(8, M+), 236(8), 198(15), 169(40),

4.3.7. (2S,6S,E)-1-methoxy-5-methyl-7-(o-
80.2, 74.7, 72.5, 59.1, 46.2, 30.9, 24.2, 22.3 (bs), 22.2, 19.5, 13.8;
(EI, m/z): 314(<5, M+), 269(15), 239(100), 198(55), 183(85),
169(95), 119(40), 55(40); HRMS (ESI) C21H30O2 [M+H]+:
315.2319 (calculated); 315.2320 (found).
ACCEPTED MANUSCRIPT
tolyl)undeca-3,5,6-trien-2-ol (3bd)
1
Isolated as a 92:8 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.26 (d, J = 6.7 Hz, 1H), 7.11-7.04 (m, 3H), 6.58
(dd, J = 15.7, 1.6 Hz, 1H), 5.54 (dd, J = 15.7, 5.9 Hz, 1H), 4.34-
4.29 (m, 1H), 3.13 (dd, A of ABX, JAB = 9.4 Hz, JAX = 7.7 Hz,
1H), 3.09 (dd, B of ABX, JAB = 9.4 Hz, JBX = 3.7 Hz, 1H), 3.00
(s, 3H), 2.35 (s, 3H), 2.33 (td, J = 7.2, 2.8 Hz, 2H), 1.80 (s, 3H),
1.50-1.42 (m, 2H), 1.36-1.26 (m, 2H), 0.84 (t, J = 7.2 Hz, 3H);
13C NMR (101 MHz, C6D6) δ: 206.9, 138.6, 136.3, 131.2, 130.9,
128.8, 127.9, 127.5, 126.6, 104.9, 100.5, 77.5, 71.6, 58.9, 34.7,
30.7, 23.1, 21.2, 16.0, 14.5; FTIR (νmax/cm-1): 3413, 2922, 1449,
1190, 1142, 959, 756, 728; MS (EI, m/z): 300(20, M+), 282(5),
225(30), 193(30), 155(50), 141(30), 105(20), 91(15), 44(100);
HRMS (ESI) C20H28O2Na [M+Na]+: 323.1982 (calculated),
323.1984 (found).
4.3.11. (2S,6S,E)-1-methoxy-5-methyl-7-(4-
(trifluoromethyl)phenyl)undeca-3,5,6-trien-2-ol
(3bg)
1
Isolated as a 92:8 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.37 (d, J = 8.2 Hz, 2H), 7.22 (d, J = 7.8 Hz, 2H),
6.54 (dd, J = 15.7, 1.6 Hz, 1H), 5.63 (dd, J = 15.7, 5.5 Hz, 1H),
4.32 (dt, J = 3.8, 1.8 Hz, 1H), 3.15 (dd, A of ABX, JAB = 11.8 Hz,
JAX = 9.6 Hz, 1H), 3.09 (dd, B of ABX, JAB = 11.8 Hz, JBX = 2.1
Hz, 1H), 3.00 (s, 3H), 2.24 (t, J = 7.2 Hz, 2H), 1.82 (s, 3H), 1.48-
1
1.40 (m, 2H), 1.36-1.27 (m, 2H), 0.88 (t, J = 7.2 Hz, 3H); H
NMR (400 MHz, CDCl3) δ: 7.53 (d, J = 8.0 Hz, 2H), 7.43 (d, J =
8.0 Hz, 2H), 6.35 (d, J = 16.0 Hz, 1H), 5.63 (dd, J = 16.0, 8.0 Hz,
1H), 4.45-4.37 (m, 1H), 3.50-3.46 (m, 1H), 3.42 (s, 3H), 3.37-
3.30 (m, 1H), 2.5 (bs, 1H), 2.44 (t, J = 8.0 Hz, 2H), 1.92 (s, 3H),
1.52-1.35 (m, 4H), 0.92 (t, J =8.0 Hz, 3H); 13C NMR (101 MHz,
CDCl3) δ: 208.8, 140.9, 130.3, 128.5 (q, JC-F = 32 Hz), 127.1,
126.3, 125.2 (q, JC-F = 16 Hz), 124.3 (q, JC-F = 270 Hz), 104.7,
103.1, 76.5, 71.2, 59.1, 29.9, 29.8, 22.4, 15.2, 14.0; 19F NMR
(326.27 MHz, CDCl3) δ: -62.4; FTIR (νmax/cm-1): 3435, 2941,
2862, 1609, 1326, 1160, 1133, 1071, 833, 612; MS (EI, m/z):
354(<1, M+), 309(35), 291(30), 267(45), 249(60), 237(90),
159(85), 109(45), 55(40), 45(100); HRMS (ESI) C20H25F3O2
[M+H]+: 355.1784 (calculated); 355.1781 (found).
4.3.8. (2S,6S,E)-1-methoxy-7-(4-methoxyphenyl)-5-
methylundeca-3,5,6-trien-2-ol (3be)
1
Isolated as a 91:9 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.38 (d, J = 9.2 Hz, 2H), 6.82 (d, J = 8.4 Hz, 2H),
6.58 (dd, J = 15.8, 1.4 Hz, 1H), 5.64 (dd, J = 15.7, 5.9 Hz, 1H),
4.37-4.32 (m, 1H), 3.33 (s, 3H), 3.16 (dd, A of ABX, JAB = 9.4
Hz, JAX = 4.3 Hz, 1H), 3.12 (dd, B of ABX, JAB = 9.4 Hz, JBX
=
7.6 Hz, 1H), 3.015 (s, 3H), 2.42 (t, J = 6.8 Hz, 2H), 1.89 (s, 3H),
1.60-1.51 (m, 2H), 1.40-1.31 (m, 2H), 0.87 (t, J = 7.2 Hz, 3H);
13C NMR (101 MHz, C6D6) δ: 208.4, 159.6, 130.9, 130.1, 128.24,
128.19, 114.7, 105.9, 103.3, 77.5, 71.7, 59.0, 55.2, 31.0, 30.9,
23.2, 16.1, 14.5; FTIR (νmax/cm-1): 3444, 2931, 2867, 1925, 1613,
1512, 1454, 1247, 1174, 1120, 1041, 967, 835, 597; MS (EI,
m/z): 316(10, M+), 259(80), 209(100), 171(95), 121(75), 44(90);
HRMS (ESI) C20H29O3 [M+H]+: 317.2111 (calculated), 317.2112
(found).
4.3.12. (2S,6S,E)-7-(3-chlorophenyl)-1-methoxy-5-
methylundeca-3,5,6-trien-2-ol (3bh)
1
Isolated as a 90:10 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.53 (t, J = 2.0 Hz, 1H), 7.17 (dd, J = 1.6, 0.8 Hz,
1H), 7.04 (ddd, J = 7.9, 2.1. 1.0 Hz, 1H), 6.87 (t, J = 8.0 Hz, 1H),
6.49 (dd, J = 15.7, 1.6 Hz, 1H), 5.60 (dd, J = 15.7, 5.9 Hz, 1H),
4.31-4.29 (m, 1H), 3.12 (dd, A of ABX, JAB = 9.4 Hz, JAX = 7.7
Hz, 1H), 3.08 (dd, B of ABX, JAB = 9.4 Hz, JBX = 3.7 Hz, 1H),
3.00 (s, 3H), 2.30 (bs, 1H), 2.22 (t, J = 7.6 Hz, 2H), 1.78 (s, 3H),
1.47-1.38 (m, 2H), 1.27 (sext, J = 7.6 Hz, 2H), 0.82 (t, J = 7.2
Hz, 3H); 13C NMR (101 MHz, C6D6) δ: 208.8, 140.2, 135.3,
130.3, 129.7, 129.1, 127.3, 126.96, 126.93,125.24, 105.4, 104.0,
77.4, 71.5, 59.0, 30.6, 30.4, 23.0, 15.7, 14.5; FTIR (νmax/cm-1):
3406, 2930, 1617, 1480, 1109, 972, 783, 686; MS (EI, m/z):
320(5, M+), 257(15), 203(45), 165(35), 125(40), 44(100); HRMS
(ESI) C19H25ClO2Na [M+Na]+: 343.1441 (calculated), 343.1439
(found).
4.3.9. (2S,6S,E)-7-(2,6-dimethylphenyl)-1-methoxy-
5-methylundeca-3,5,6-trien-2-ol (3bf)
1
Isolated as a 74:26 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.06-6.96 (m, 3H), 6.65 (d, J = 15.8 Hz, 1H), 5.52
(dd, 15.8, 5.9, 1H), 4.35-4.31 (m, 1H), 3.13 (dd, A of ABX, JAB
=
9.2 Hz, JAX = 7.8 Hz, 1H), 3.08 (dd, B of ABX, JAB = 9.2 Hz, JBX
= 3.5 Hz, 1H), 3.00 (s, 3H), 2.34 (s, 6H), 2.13-2.07 (m, 2H), 1.77
(s, 3H), 1.55-1.48 (m, 2H), 1.37-1.26 (m, 2H), 0.85 (t, J = 7.2 Hz,
3H); 13C NMR (101 MHz, C6D6) δ: 204.8, 138.9, 136.0, 130.7,
128.3, 127.7, 127.5, 104.1, 100.8, 77.5, 71.6, 58.9, 34.1, 30.5,
23.3, 20.8, 15.7, 14.6; FTIR (νmax/cm-1): 3421, 2944, 1470, 1386,
1190, 1129, 956, 760; MS (EI, m/z): 314(50, M+), 269(60),
197(45), 157(30), 119(55), 45(100); HRMS (ESI) C21H31O2
[M+H]+: 315.2319 (calculated); 315.2320 (found).
4.3.13. (2S,6S,E)-7-(2-fluorophenyl)-1-methoxy-5-
methylundeca-3,5,6-trien-2-ol (3bi)
1
Isolated as a 92:8 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.25-7.21 (m, 1H), 6.85-6.80 (m, 3H), 6.59 (dd, J
= 15.9, 1.4 Hz, 1H), 5.59 (dd, J = 15.9, 5.9 Hz, 1H), 4.33-4.29
(m, 1H), 3.13 (dd, A of ABX, JAB = 9.4 Hz, JAX = 8.2 Hz, 1H),
3.09 (dd, B of ABX, JAB = 9.4 Hz, JBX = 3.6 Hz, 1H), 3.00 (s,
3H), 2.47 (t, J = 7.4 Hz, 2H), 2.30 (bs, 1H), 1.85 (s, 3H), 1.52-
1.44 (m, 2H), 1.32 (sext, J = 8.0 Hz, 2H), 0.83 (t, J = 7.2 Hz,
3H); 1H NMR (400 MHz, CDCl3) δ: 7.27-7.15 (m, 2H), 7.09-6.98
(m, 2H), 6.36 (d, J = 16.0 Hz, 1H), 5.55 (dd, J = 16.0, 8.0 Hz,
1H), 4.42-4.37 (m, 1H), 3.49-3.45 (m, 1H), 3.41 (s, 3H),
3.36−3.31 (m, 1H), 2.42 (t, J =8.0 Hz, 2H), 1.87 (s, 3H), 1.65 (bs,
1H), 1.43-1.19 (m, 4H), 0.89 (t, J = 8.0 Hz, 3H); 13C NMR (101
MHz, CDCl3) δ: 208.7, 160.2 (d, JC-F = 247.3 Hz), 131.3, 129.8
4.3.10. (Z)-3-(2,6-dimethylphenyl)-1-methoxy-5-
methylundec-4-en-6-yn-2-ol (4bf)
1H NMR (400 MHz, C6D6) δ: 7.05-6.96 (m, 3H), 6.35 (d, J =
8.0 Hz, 1H), 4.69 (t, J = 8.0 Hz, 1H), 4.31-4.23 (m, 1H), 3.20-
3.16 (dd, J = 9.4, 2.8 Hz, 1H), 3.14-3.07 (m, 1H), 2.92 (s, 3H),
2.69-2.28 (bs, 6H), 2.11 (t, J = 6.8 Hz, 2H), 1.87 (s, 3H), 1.40-
1.18 (m, 4H), 0.77 (t, J = 8.0 Hz, 3H); FTIR (νmax/cm-1): 3451,
2912, 1460, 1391, 1122, 767; 13C NMR (101 MHz, C6D6) δ:
139.5, 137.1, 126.9, 120.8, 95.2, 81.4, 75.4, 73.1, 58.9, 46.7,
31.5, 24.5, 22.8 (bs), 22.6, 20.0, 14.1; 1H NMR (400 MHz,
CD3Cl) δ: 7.02-6.97 (m, 3H), 6.14 (d, J = 8.0 Hz, 1H), 4.43 (t, J
= 8.0 Hz, 1H), 4.29-4.22 (m, 1H), 3.28 (s, 3H), 3.28-3.22 (m,
1H), 3.14-3.09 (m, 1H), 2.43 (s, 6H), 2.29 (t, J = 8.0 Hz, 2H),
1.86 (s, 3H), 1.51-1.33 (m, 4H), 0.90 (t, J = 8.0 Hz, 3H); 13C
NMR (101 MHz, CD3Cl) δ: 138.0, 135.0, 126.5, 121.3, 95.1,
(d, JC-F = 3.8 Hz), 128.4 (d, JC-F = 8.3 Hz), 126.4, 125.7 (d, JC-F
=
12.9 Hz), 124.0 (d, JC-F = 3.8 Hz), 116.1 (d, JC-F = 22.8 Hz),
100.7, 100.5, 76.7, 71.4, 59.2, 32.0, 30.2, 22.4, 15.5, 14.1; 19F
NMR (326.27 MHz, CDCl3) δ: -114.0; FTIR (νmax/cm-1): 3425,
2923, 1487, 1440, 1196, 1110, 971, 752; MS (EI, m/z): 304(5,

8
Tetrahedron
ACCEPTED MANUSCRIPT
M+), 259(15), 199(25), 187(60), 133(25), 109(100), 45(35);
0.88 (t, J = 7.6 Hz, 3H); 13C NMR (101 MHz, C6D6) δ: 212.4,
HRMS (ESI) C19H26FO2 [M+H]+: 305.1911 (calculated),
305.1913 (found).
138.4, 130.4, 129.2, 127.84, 127.80, 127.0, 106.0, 101.6, 77.4,
71.6, 59.0, 30.6, 29.4, 23.2, 16.1, 14.6; FTIR (νmax/cm-1): 3435,
2923, 1460, 1142, 957, 753, 693; MS (EI, m/z): 312(40), 267(35),
223(15), 195(80), 165(60), 115(50), 91(100), 32(60); HRMS
(ESI) C21H29O2 [M+H]+: 313.2161 (calculated), 313.2178
(found).
4.3.14. (2S,6S,E)-1-methoxy-5-methyl-7-
(naphthalen-1-yl)undeca-3,5,6-trien-2-ol (3bj)
1
Isolated as a 91:9 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 8.39 (d, J = 8.6 Hz, 1H), 7.66 (dd, J = 8.2, 0.8 Hz,
1H), 7.57 (d, J = 8.2 Hz, 1H), 7.41-7.37 (m, 2H), 7.29-7.24 (m,
2H), 6.67 (dd, J = 15.8, 1.4 Hz, 1H), 5.54 (dd, J = 15.8, 5.7 Hz,
4.3.18. (E)-4-methyl-6-phenyldeca-2,4,5-trien-1-ol
(3ca)
1H), 4.35-4.30 (m, 1H), 3.13 (dd, A of ABX, JAB = 9.4 Hz, JAX
=
1H NMR (400 MHz, C6D6) δ: 7.45 (d, J = 8.0 Hz, 2H), 7.19 (t,
J = 7.8 Hz, 2H), 7.07 (td, J = 7.6, 0.8 Hz, 1H), 6.29 (d, J = 15.6
Hz, 1H), 5.59 (dtd, J = 15.6, 5.8, 0.8 Hz, 1H), 3.90 (d, J = 5.8 Hz,
2H), 2.41 (t, 7.4 Hz, 2H), 1.83 (s, 3H), 1.54 (quin, J = 7.4 Hz,
2H), 1.39-1.30 (m, 2H), 0.87 (t, J = 7.6 Hz, 3H); 13C NMR (101
MHz, C6D6) δ: 208.6, 138.0, 129.7, 129.12, 129.07, 127.4, 127.0,
106.3, 103.4, 63.8, 30.8, 30.7, 23.2, 15.9, 14.5; FTIR (νmax/cm-1):
3345, 2912, 1488, 1449, 1305, 978, 689; MS (EI, m/z): 242(<5,
M+), 224(5), 200(15), 169(100), 154(20), 141(25), 128(20),
115(20), 91(30), 41(5); HRMS (ESI) C17H22ONa [M+Na]+:
265.1563 (calculated), 265.1569 (found).
8.1 Hz, 1H), 3.08 (dd, B of ABX, JAB = 9.4 Hz, JBX = 3.7 Hz, 1H),
3.00 (s, 3H), 2.47 (td, J = 7.5, 1.8 Hz, 2H), 1.84 (s, 3H), 1.524
(quint, J = 7.2 Hz, 2H), 1.33 (sext, J = 7.6 Hz, 2H), 0.83 (t, J =
7.6 Hz, 3H); 13C NMR (101 MHz, C6D6) δ: 207.3, 137.6, 135.0,
132.4, 130.8, 129.2, 128.1, 126.6, 126.4, 126.32, 126.1, 104.5,
100.7, 77.5, 71.6, 58.9, 35.5, 31.0, 23.1, 16.1, 14.5; FTIR
(νmax/cm-1): 3435, 2922, 1946, 1470, 1206, 1129, 986, 804, 782;
MS (EI, m/z): 336 (20, M+), 273(30), 261(55), 229(100), 217(65),
202(80), 165(60), 141(35), 44(95); HRMS (ESI) C23H28O2Na
[M+Na]+: 359.1982 (calculated), 359.1983 (found).
4.3.15. (2S,6S,E)-1-methoxy-5-methyl-7-
(naphthalen-2-yl)undeca-3,5,6-trien-2-ol (3bk)
4.3.19. (2S,6S,E)-5-methyl-7-phenylundeca-3,5,6-
triene-1,2-diol (3da)
1
1
Isolated as a 91:9 mixture of diastereomers; H NMR (400
Isolated as a 91:9 mixture of diastereomers; H NMR (400
MHz, C6D6): δ 7.84 (s, 1H), 7.71 (dd, J = 8.4, 1.6 Hz, 1H), 7.68-
7.60 (m, 3H), 7.26 (quint, J = 7.1, 1.6 Hz, 2H), 6.62 (dd, J =
15.8, 1.4 Hz, 1H), 5.67 (dd, J = 15.8, 5.9 Hz, 1H), 4.37-4.33 (m,
1H), 3.15 (dd, A of ABX, JAB = 9.4 Hz, JAX = 7.8 Hz, 1H), 3.12
(dd, B of ABX, JAB = 9.4 Hz, JBX = 3.5 Hz, 1H), 3.01 (s, 3H),
2.52 (t, J = 7.6 Hz, 2H), 2.35 (bs, 1H), 1.91 (s, 3H), 1.63-1.56 (m,
2H), 1.38 (sext, J = 7.6 Hz, 2H), 0.89 (t, J = 7.2 Hz, 3H); 13C
NMR (101 MHz, C6D6): δ 209.6, 135.4, 134.7, 133.5, 130.3,
128.8, 128.7, 126.7, 126.5, 126.3, 124.6, 106.6, 103.8, 77.5, 71.7,
59.0, 30.8, 30.7, 23.2, 16.0, 14.6; FTIR (νmax/cm-1): 3451, 2950,
1449, 1363, 1122, 959, 863, 825, 747; MS (EI, m/z): 336(15,
M+), 291(30), 261(30), 219(80), 207(55), 165(45), 141(100),
73(50), 45(60); HRMS (ESI) C23H28O2Na [M+Na]+: 359.1982
(calculated), 359.1983 (found).
MHz, C6D6) δ: 7.45-7.42 (m, 2H), 7.21-7.16 (m, 2 H), 7.08-7.04
(m, 1H), 6.42 (dd, J = 15.6, 1.6 Hz, 1H), 5.50 (dd, J = 15.6, 6.4
Hz, 1H), 4.05-4.02 (m, 1H), 3.40-3.37 (m, 1H), 3.30-3.24 (m,
1H), 2.40 (t, J = 7.4 Hz, 2H), 1.82 (d, J = 0.8 Hz, 3H), 1.55-1.48
(m, 2H), 1.38-1.28 (m, 2H), 0.86 (t, J = 7.6 Hz, 3H); 13C NMR
(101 MHz, C6D6) δ: 208.9, 137.9, 130.9, 129.1, 127.4, 127.1,
106.4, 103.3, 73.8, 67.2, 30.8, 30.7, 23.2, 15.9, 14.5; MS (EI,
m/z): 256(25), 239(27), 112(95), 83(40), 70(75), 57(100), 43(65);
FTIR (νmax/cm-1): 3365, 2951, 2920, 2862, 1925, 1597, 1454,
1079, 1031, 967, 750, 698; HRMS (ESI) C18H25O2 [M+H]+:
273.1849 (calculated), 273.1851 (found).
4.3.20. (2S,6S,E)-1-(benzyloxy)-5-methyl-7-
phenylundeca-3,5,6-trien-2-ol (3ea)
1
4.3.16. (2S,3E,6S,8E)-7-butyl-1-methoxy-5-
Isolated as a 90:10 mixture of diastereomers; H NMR (400
methyldodeca-3,5,6,8-tetraen-2-ol (3bl)
MHz, C6D6) δ: 7.44 (d, J = 7.8 Hz, 2H), 7.20-7.14 (m, 6H), 7.11-
7.05 (m, 2H), 6.57 (d, J = 15.9 Hz, 1H), 5.60 (dd, J =15.9, 5.9
Hz, 1H), 4.39-4.34 (m, 1H), 4.24 (s, 2H), 3.28 (dd, A of ABX,
JAB = 9.3 Hz, JAX = 7.9 Hz, 1H), 3.21 (dd, B of ABX, JAB = 9.3
Hz, JBX = 3.8 Hz, 1H), 2.39 (t, J = 7.2 Hz, 2H), 2.25 (bs, 1H),
1.85 (s, 3H), 1.51 (quint, J = 7.4 Hz, 2H), 1.32 (sext, J = 7.6 Hz,
2H), 0.85 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, C6D6) δ:
208.8, 139.0, 137.9, 130.5, 129.1, 129.0, 128.5, 128.3, 128.2,
127.4, 127.1, 106.3, 103.4, 75.1, 73.6, 71.8, 30.8, 30.7, 23.2,
15.9, 14.5; FTIR (νmax/cm-1): 3435, 2915, 1503, 1450, 1142, 983,
763, 674; MS (EI, m/z): 362(<5, M+), 320(5), 253(10), 197(20),
181(25), 169(45), 129(20), 91(100), 69(35), 41(40); HRMS (ESI)
C25H30O2Na [M+Na]+: 385.2138 (calculated), 385.2138 (found).
1
Isolated as a 83:17 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 6.53 (dd, J = 15.1, 1.0 Hz, 1H), 6.09 (d, J = 16.0
Hz, 1H), 5.65 (dt, J = 15.7, 7.0 Hz, 1H), 5.58 (dd, J = 15.7, 5.6
Hz, 1H,), 4.33-4.29 (m, 1H), 3.13 (dd, A of ABX, JAB = 9.5 Hz,
JAX = 7.8 Hz, 1H), 3.09 (dd, B of ABX, JAB = 9.5 Hz, JBX = 4.0
Hz, 1H), 3.00 (s, 3H), 2.20 (t, J = 7.2 Hz, 2H), 2.02 (q, J = 6.5
Hz, 2H), 1.84 (s, 3H), 1.56-1.48 (m, 2H), 1.39-1.29 (m, 4H), 0.87
(t, J = 7.6 Hz, 3H), 0.85 (t, J = 7.6 Hz, 3H); 13C NMR (101 MHz,
C6D6) δ: 210.5, 131.0, 129.6, 128.7, 127.8, 105.3, 101.2, 77.5,
71.6, 58.9, 35.8, 30.7, 29.6, 23.4, 23.3, 16.2, 14.6, 14.3; FTIR
(νmax/cm-1): 3442, 2927, 1480, 1261, 1113, 958, 796; MS (EI,
m/z): 278(10), 233(25), 161(30), 119(45), 105(100), 93(60),
55(55); HRMS (ESI) C19H32O2Na [M+Na]+: 315.2319
(calculated), 315.2320 (found).
4.3.21. (2S,6S,E)-1-((tert-butyldimethylsilyl)oxy)-5-
4.3.17. (2S,6S,E)-1-methoxy-5-methyl-7-((E)-
methyl-7-phenylundeca-3,5,6-trien-2-ol (3fa)
styryl)undeca-3,5,6-trien-2-ol (3bm)
1
Isolated as a 92:8 mixture of diastereomers; H NMR (400
1
Isolated as a 70:30 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.44 (d, J = 7.6 Hz, 2H), 7.19 (t, J = 8.0 Hz, 2H),
7.07 (t, J = 7.4 Hz, 1H), 6.58 (dd, J = 15.9, 1.2 Hz, 1H), 5.65 (dd,
MHz, C6D6) δ: 7.27-7.23 (m, 2H), 7.12 (t, J = 7.8 Hz, 2H), 7.05-
7.02 (m, 1H), 6.83 (d, J = 16.4 Hz, 1H), 6.58 (d, J = 16.4 Hz,
1H), 6.57 (dd, J = 15.8, 0.4 Hz, 1H), 5.64 (ddd, J = 16.0, 5.6, 0.8
Hz, 1H), 5.64 (ddd, J=16.0, 5.6, 0.8 Hz, 1H), 4.36-4.31 (m, 1H),
3.14 (dd, A of ABX, JAB = 9.4 Hz, JAX = 7.7 Hz, 1H), 3.10 (dd, B
of ABX, JAB = 9.4 Hz, JBX = 3.6 Hz, 1H), 3.00 (s, 3H), 2.26 (t, J =
7.2 Hz, 2H), 1.86 (s, 3H), 1.57-1.50 (m, 2H), 1.39-1.30 (m, 2H),
J = 15.9, 6.1 Hz, 1H), 4.25 (bs, 1H), 3.53 (dd, A of ABX, JAB
=
9.9 Hz, JAX = 7.3 Hz, 1H), 3.43 (dd, B of ABX, JAB = 9.9 Hz, JBX
= 3.7 Hz, 1H), 2.39 (t, J = 7.6 Hz, 2H), 2.32 (d, J = 3.1 Hz, 1H),
1.89 (s, 3H), 1.52 (quint, J =7.6 Hz, 2H), 1.38-1.29 (m, 2H), 0.91
(s, 9H), 0.86 (t, J = 7.2 Hz, 3H), -0.01 (s, 6H); 13C NMR (101

MHz, C6D6) δ: 208.8, 137.9, 134.9, 131.5, 130.6, 129.1, 127.4,
138.1, 130.4, 129.0, 128.7, 127.3, 126.7, 102.2, 101.0, 77.4, 71.7,
59.0, 17.5, 15.8; FTIR (νmax/cm-1): 3432, 2922, 1498, 1449, 1135,
1027, 978, 767, 689, 593; MS (EI, m/z): 244(10, M+), 199(100),
181(35), 166(45), 128(35), 105(20), 91(30), 77(20), 45(25);
HRMS (ESI) C16H21O2 [M+H]+: 245.1535 (calculated), 245.1536
(found).
ACCEPTED MANUSCRIPT
127.1, 106.3, 103.4, 73.5, 68.2, 30.8, 30.7, 26.4, 23.2, 21.9, 18.8,
16.0, 14.5, -4.9; FTIR (νmax/cm-1): 3426, 2915, 1468, 1318, 1256,
1115, 851, 772, 683; MS (EI, m/z): 386(<1, M+), 311(5), 237(30),
195(35), 181(55), 169(30), 105(35), 91(55), 75(100); HRMS
(ESI) C24H39O2Si [M+H]+: 387.2714 (calculated), 387.2716
(found).
4.3.26. (2S,6S,E)-1-methoxy-7-(4-methoxyphenyl)-
5-methyl-7-phenylhepta-3,5,6-trien-2-ol (3ke)
4.3.22. (3S,7S,E)-2-methoxy-2,6-dimethyl-8-
1
phenyldodeca-4,6,7-trien-3-ol (3ga)
Isolated as a 91:9 mixture of diastereomers; H NMR (400
1
Isolated as a 92:8 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.52-7.46 (m, 2H), 7.40-7.36 (m, 1H), 7.38 (d, J =
8.8 Hz, 1H), 7.18-7.14 (m, 2H), 7.10-7.06 (m, 1H), 6.79-6.75 (m,
1H), 6.77 (d, J = 8.4 Hz, 1H), 6.58 (dd, J = 15.8, 1.4 Hz, 1H),
5.63 (dd, J = 15.8, 5.9 Hz, 1H), 4.30 (q, J = 5.6 Hz, 1H), 3.29 (s,
3H), 3.11 (dd, A of ABX, JAB = 8.6 Hz, JAX = 5.8 Hz, 1H), 3.08
(dd, B of ABX, JAB = 8.6 Hz, JBX = 2.4 Hz, 1H), 3.00 (s, 3H),
2.31 (bs, 1H), 1.85 (s, 3H); 13C NMR (101 MHz, C6D6) δ: 210.5,
160.0, 138.2, 130.59, 130.0, 129.9, 129.43, 129.2, 129.1, 127.9,
114.7, 110.3, 103.2, 77.4, 71.6, 59.0, 55.2, 16.0; FTIR (νmax/cm-
1): 3432, 2931, 1507, 1267, 1180, 1122, 1036, 978, 834, 767,
700; MS (EI, m/z): 336 (30, M+), 291(100), 262(65), 247(40),
183(30), 155(25), 30(25), 45(45); HRMS (ESI) C22H25O3
[M+H]+: 337.1798 (calculated), 337.1799 (found).
MHz, C6D6) δ: 7.44 (d, J = 7.2 Hz, 2H), 7.43 (d, J = 7.2 Hz, 2H,
minor), 7.18 (t, J = 7.6 Hz, 2H), 7.06 (t, J = 7.2 Hz, 1H), 6.54 (d,
J = 15.6 Hz, 1H), 5.77 (ddd, J = 15.7, 6.6, 0.8 Hz, 1H), 4.06 (d, J
= 6.4 Hz, 1H), 2.92 (s, 3H), 2.55 (bs, 1H), 1.879 (s, 3H), 1.51
(quint, J = 7.6 Hz, 2H), 1.32 (sext, J = 7.6 Hz, 2H), 1.03 (s, 3H),
0.97 (s, 3H), 0.85 (t, J = 7.6 Hz, 3H); 13C NMR (101 MHz, C6D6)
δ: 208.7, 138.0, 134.9, 131.3, 129.1, 127.3, 127.1, 106.2, 103.5,
78.7, 78.0, 72.4, 49.4, 30.8, 23.1, 21.9, 21.1, 19.9, 16.0, 14.5;
FTIR (νmax/cm-1): 3438, 2920, 1480, 1384, 1067, 962, 761, 708;
MS (EI, m/z): 314(<1, M+), 242(5), 91(5), 115(5), 73(100);
HRMS (ESI) C21H31O2 [M+H]+: 315.2318 (calculated), 315.2327
(found).
4.3.23. (2R,6S,E)-5-methyl-7-phenylundeca-3,5,6-
4.3.27. methyl (3R,7S,E)-7-hydroxy-8-methoxy-4-
trien-2-ol (3ha)
methyl-2-phenylocta-2,3,5-trienoate (3la)
1
1
Isolated as a 91:9 mixture of diastereomers; H NMR (400
Isolated as a 89:11 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.46 (d, J = 8.0 Hz, 2H), 7.19 (t, J = 7.6 Hz, 2H),
7.07 (t, J = 7.2 Hz, 1H), 6.30 (d, J = 15.7 Hz, 1H), 5.59 (ddd, J =
15.7, 6.4, 0.8 Hz, 1H), 4.14-4.08 (m, 1H), 2.42 (t, J = 7.2 Hz,
2H), 1.85 (d, J = 0.8 Hz, 3H), 1.54 (quint, J = 7.2 Hz, 2H), 1.39-
1.30 (m, 2H), 1.12 (d, J = 6.4 Hz, 3H), 0.86 (t, J = 7.2 Hz, 3H);
13C NMR (101 MHz, C6D6) δ: 208.7, 138.0, 134.1, 129.1, 128.3,
127.4, 127.0, 106.2, 103.3, 69.0, 30.8, 30.7, 24.1, 23.15, 16.0,
14.5; FTIR (νmax/cm-1): 3332, 2972, 2920, 1501, 1427, 1089, 982,
782, 708; MS (EI, m/z): 256(<5, M+), 238(5), 196(10), 181(15),
169(100), 155(25), 141(25), 129(20), 115(20), 91(25), 77(10),
43(25); HRMS (ESI) C18H25O [M+H]+: 257.1899 (calculated),
257.1907 (found).
MHz, C6D6) δ: 7.74-7.70 (m, 2H), 7.18-7.12 (m, 2H), 7.05-7.01
(m, 1H), 6.38 (dd, J = 15.8, 1.2 Hz, 1H), 5.55 (dd, J = 15.8, 5.6
Hz, 1H), 4.20-4.14 (m, 1H), 3.36 (s, 3H), 3.00−2.93 (m, 2H),
2.94 (s, 3H), 2.04 (bs, 1H), 1.68 (s, 3H); 13C NMR (101 MHz,
C6D6) δ: 216.7, 166.5, 139.9, 131.1, 129.4, 129.0, 128.3, 127.0,
105.2, 103.4, 77.1, 71.4, 59.0, 52.2, 15.0; MS (EI, m/z): 288(<5,
M+), 256 (3), 211 (5), 183(5), 155 (17), 115 (8), 89 (4), 77 (9), 51
(5), 45 (100); FTIR (νmax/cm−1): 3419, 2922, 2851, 1926, 1716,
1492, 1434, 1369, 1321, 1273, 1195, 1171, 1123, 1062, 1039,
964, 918, 898, 781, 694; HRMS (ESI) C17H21O4 [M+H]+:
289.1434 (calculated), 289.1439 (found).
4.3.28. (2S,6S,E)-7-cyclohexyl-1-methoxy-5-methyl-
7-phenylhepta-3,5,6-trien-2-ol (3ma)
4.3.24. (2S,6S,E)-1-methoxy-5-methyl-7-
phenylhepta-3,5,6-trien-2-ol (3ia)
1
Isolated as a 92:8 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.43 (d, J = 8.2 Hz, 2H), 7.19 (d, J = 7.2 Hz, 2H),
7.08-7.04 (m, 1H), 6.57 (d, J = 15.7 Hz, 1H), 5.63 (ddd, J = 15.7,
1
Isolated as a 91:9 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.23 (d, J = 6.8 Hz, 2H), 7.11 (t, J = 7.6 Hz, 2H),
7.01 (t, J = 7.2 Hz, 1H), 6.49 (d, J = 16.0 Hz, 1H), 6.20 (s, 1H),
5.62 (ddt, J = 15.6, 5.6, 1.2 Hz, 1H), 4.28 (bs, 1H), 3.11-3.08 (m,
1H), 3.00 (s, 3H), 3.02-2.90 (m, 1H), 2.16 (bs, 1H), 1.80 (s, 3H);
13C NMR (101 MHz, C6D6) δ: 210.0, 135.4, 129.3, 128.6, 128.3,
127.7, 127.59, 110.7, 104.1, 77.3, 71.6, 59.0, 15.7; FTIR
(νmax/cm-1): 3412, 2929, 1506, 1471, 1118, 966, 753, 683; MS
(EI, m/z): 230(15, M+), 185(100), 165(30), 152(45), 129(60),
115(50), 91(40), 77(30), 45(30); HRMS (ESI) C15H19O2 [M+H]+:
231.1379 (calculated), 231.1385 (found).
5.9, 0.8 Hz, 1H), 4.36-4.32 (m, 1H), 3.15 (dd, A of ABX, JAB
=
9.2 Hz, JAX = 7.7 Hz, 1H), 3.11 (dd, B of ABX, JAB = 9.2 Hz, JBX
= 3.6 Hz, 1H), 3.01 (s, 3H), 1.48-1.41 (m, 1H), 2.34 (bs, 1H),
1.96-1.93 (m, 2H), 1.86 (d, J = 0.8 Hz, 3H), 1.72-1.58 (m, 3H),
1.30-1.08 (m, 5H); 13C NMR (101 MHz, C6D6) δ: 208.6, 137.7,
130.7, 129.1, 128.3, 127.6, 127.3, 112.7, 104.2, 77.5, 71.7, 59.0,
39.3, 33.8, 33.8, 27.3, 27.3, 27.0, 16.1; FTIR (νmax/cm-1): 3444,
2923, 2858, 1506, 1458, 1123, 953, 774, 701; MS (EI, m/z):
312(10, M+), 267(70), 181(100), 141(50), 91(80), 45(60); HRMS
(ESI) C21H29O2 [M+H]+: 313.2161 (calculated), 313.2178
(found).
4.3.25. (2S,6S,E)-1-methoxy-5-methyl-7-phenylocta-
3,5,6-trien-2-ol (3ja)
1
Isolated as a 92:8 mixture of diastereomers; H NMR (400
4.3.29. (2S,6S,E)-1-methoxy-5,8,8-trimethyl-7-
phenylnona-3,5,6-trien-2-ol (3na)
MHz, C6D6) δ: 7.39 (d, J = 8.4 Hz, 2H), 7.16 (t, J = 7.6 Hz, 2H),
7.05 (t, J = 7.6 Hz, 1H), 6.51 (d, J = 15.6 Hz, 1H), 5.63 (ddd, J =
15.8, 5.9, 0.8 Hz, 1H), 4.33-4.29 (m, 1H), 3.13 (dd, A of ABX,
JAB = 8.7 Hz, JAX = 6.8 Hz, 1H), 3.11 (dd, B of ABX, JAB = 8.7
Hz, JBX = 3.4 Hz, 1H), 3.01 (s, 3H), 2.36 (bs, 1H), 1.97 (s, 3H),
1.83 (d, J = 0.8 Hz, 3H); 13C NMR (101 MHz, C6D6) δ: 208.9,
1
Isolated as a 92:8 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.30-7.27 (m, 2H), 7.14-7.12 (m, 2H), 7.09-7.05
(m, 1H), 6.59 (dd, J = 15.7, 1.2 Hz, 1H), 5.51 (dd, J = 16.0, 4.3
Hz, 1H), 4.35-4.31 (m, 1H), 3.13 (dd, A of ABX, JAB = 9.3 Hz,
JAX = 8.1 Hz, 1H), 3.08 (dd, B of ABX, JAB = 9.3 Hz, JBX = 3.7

10
Tetrahedron
Hz, 1H), 3.00 (s, 3H), 2.24 (bs, 1H), 1.77 (s, 3H), 1.16 (s,
J
= 9.5 Hz, J = 8.9 Hz, 1H), 3.10 (dd, B of ABX, J = 9.5
ACCEPTED MANUSCRIPT
AB AX AB
9H); 13C NMR (101 MHz, C6D6) δ: 206.1, 138.5, 131.2, 130.2,
128.9, 128.5, 127.7, 127.3, 127.1, 100.9, 77.5, 71.6, 58.9, 35.7,
31.8, 30.5, 16.4; FTIR (νmax/cm-1): 3422, 2960, 1460, 1199, 1132,
969, 709; MS (EI, m/z): 286 (10, M+), 241(75), 197(100),
165(35), 141(40), 105(85), 57(95); HRMS (ESI) C19H27O2
[M+H]+: 287.2005 (calculated), 287.2016 (found).
Hz, JBX = 4.0 Hz, 1H), 2.99 (s, 3H), 2.46-2.42 (m, 2H), 2.29 (bs,
1H), 2.26-2.22 (m, 1H), 2.07-2.04 (m, 2H), 1.71-1.56 (m, 4H),
1.39-1.06 (m, 7H), 0.88 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz,
C6D6) δ: 207.1, 138.0, 129.1, 128.9, 128.3, 127.3, 126.7, 114.4,
109.0, 77.5, 71.8, 58.9, 39.3, 33.8, 33.7, 31.1, 30.8, 27.3, 27.3,
27.0, 23.4, 14.5; FTIR (νmax/cm-1): 3446, 2918, 2846, 1424, 1142,
1000, 777, 683; MS (EI, m/z): 336(10), 309(35), 279(45),
207(40), 155(50), 91(100), 55(55), 32(55); HRMS (ESI)
C24H35O2 [M+H]+: 355.2631 (calculated), 355.2642 (found).
4.3.30. (Z)-1-methoxy-5,8,8-trimethyl-3-phenylnon-
4-en-6-yn-2-ol (4na)
1H NMR (400 MHz, C6D6) δ: 7.40 (d, 7.8 Hz, 2H), 7.20 (d, J
= 7.6 Hz, 2H), 7.07 (t, J = 7.6 Hz, 1H), 6.12 (dd, J = 9.6, 1.4 Hz,
1H), 4.26 (dd, J = 9.8, 6.0 Hz, 1H), 4.10-4.06 (m, 1H), 3.30 (dd,
A of ABX, JAB = 9.4 Hz, JAX = 7.1 Hz, 1H), 3.23 (dd, B of ABX,
JAB = 9.4 Hz, JBX = 3.4 Hz, 1H), 3.00 (s, 3H), 2.22 (s, 1H), 1.80
(s, 3H), 1.23 (s, 9H); 13C NMR (101 MHz, C6D6) δ: 143.4, 136.4,
129.1, 128.3, 127.0, 121.1, 102.8, 79.7, 75.8, 74.6, 59.0, 50.4,
31.6, 28.6, 24.0; FTIR (νmax/cm-1): 3446, 2910, 1459, 1364, 1117,
1079, 688; MS (EI, m/z): 268(5), 212(100), 197(65), 169(65),
155(95), 141(35), 91(55), 41(40).
4.3.34. (Z)-5-cyclohexyl-1-methoxy-3-phenylundec-
4-en-6-yn-2-ol (4qa)
1H NMR (400 MHz, C6D6) δ: 7.45 (d, J = 7.8 Hz, 2H), 7.20 (t,
J = 7.8 Hz, 2H), 7.08 (t, J = 7.2 Hz, 1H), 6.22 (d, J = 9.8 Hz,
1H), 4.34 (dd, J = 9.8, 5.5 Hz, 1H), 4.14 (bs, 1H), 3.39-3.25 (m,
2H), 3.04 (s, 3H), 2.21 (t, J = 6.4 Hz, 2H), 2.08 (t, J = 12.0 Hz,
1H), 1.84 (dd, J = 26.4, 12.4 Hz, 2H), 1.71-1.65 (m, 2H), 1.58-
1.29 (m, 7H), 1.22-1.08 (m, 3H), 0.82 (t, J = 6.8 Hz, 3H); 13C
NMR (101 MHz, C6D6) δ: 143.6, 132.2, 129.1, 129.0, 128.3,
127.0, 95.9, 79.6, 75.9, 74.6, 59.1, 49.9, 46.4, 33.1, 32.9, 31.7,
27.1, 27.0, 26.8, 22.6, 19.9, 14.1; FTIR (νmax/cm-1): 3469, 2940,
1459, 1269, 1089, 876, 697; MS (EI, m/z): 336(<5), 279(65),
223(55), 197(60), 155(100), 115(40), 91(85), 55(35).
4.3.31. (2S,6S,E)-1-methoxy-7-phenylundeca-3,5,6-
trien-2-ol (3oa)
1
Isolated as a 89:11 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.44 (d, J = 7.0 Hz, 2H), 7.18 (t, J = 7.2 Hz, 2H),
7.06 (t, J = 7.2 Hz, 1H), 6.37 (ddd, J = 15.3, 10.6, 1.2 Hz, 1H),
6.16 (dt, J = 10.6, 2,9 Hz, 1H), 5.61 (dd, J = 15.5, 5.7 Hz, 1H),
4.27-4.23 (m, 1H), 3.09 (dd, A of ABX, JAB = 9.4 Hz, JAX = 8.1
Hz, 1H), 3.05 (dd, B of ABX, JAB = 9.4 Hz, JBX = 3.6 Hz, 1H),
2.98 (s, 3H), 2.39-2.34 (m, 2H), 2.24 (bs, 1H), 1.52 (quint, J =
7.2 Hz, 2H), 1.32 (sext, J = 7.6 Hz, 2H), 0.85 (t, J = 7.6 Hz, 3H);
13C NMR (101 MHz, C6D6) δ: 209.0, 137.3, 131.6, 129.1, 128.5,
127.5, 127.1, 108.2, 97.6, 77.2, 71.3, 58.9, 30.8, 30.5, 23.2, 14.5;
FTIR (νmax/cm-1): 3426, 2932, 1450, 1133, 974, 772, 701; MS
(EI, m/z): 272(<5, M+); 254(5), 227(20), 209(20), 185(65),
167(55), 155(75), 141(70), 129(65), 115(70), 91(100), 77(30),
45(50).
4.3.35. (2S,6R,E)-5-(tert-butyl)-1-methoxy-7-
phenylundeca-3,5,6-trien-2-ol (3ra)
1
Isolated as a 85:15 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.52 (d, J = 7.6 Hz, 2H), 7.21 (t, J = 7.6 Hz, 2H),
7.06 (t, J = 8.0 Hz, 1H), 6.42 (dd, J = 15.5, 1.4 Hz, 1H), 6.02 (dd,
J = 15.6, 5.2 Hz, 1H), 4.31 (bs, 1H), 3.04 (dd, A of ABX, JAB
=
7.7 Hz, JAX = 7.3 Hz, 1H), 3.01 (dd, B of ABX, JAB = 7.7 Hz, JBX
= 1.3 Hz, 1H), 2.93 (s, 3H), 2.47-2.42 (m, 2H), 2.24 (bs, 1H),
1.61 (quint, J = 7.6 Hz, 2H), 1.55 (s, 3H), 1.39-1.33 (m, 2H),
1.19 (s, 9H), 0.89 (t, J=7.6 Hz, 3H); 13C NMR (101 MHz, C6D6):
δ 203.0, 138.2, 130.8, 129.2, 128.3, 127.2, 126.4, 125.7, 117.3,
109.3, 77.4, 71.5, 58.8, 34.9, 31.0, 30.8, 30.1, 23.4, 14.6; FTIR
(νmax/cm-1): 3421, 2867, 1453, 1379, 1242, 1155, 806, 701; MS
(EI, m/z): 309(<5), 253(20), 212(20), 197(65), 155(95), 140(60),
105(40), 91(100), 69(40), 57(95).
4.3.32. (2S,6S,E)-5-butyl-1-((tert-
butyldimethylsilyl)oxy)-7-phenylundeca-3,5,6-trien-
2-ol (3pa)
1
Isolated as a 92:8 mixture of diastereomers; H NMR (400
4.3.36. (Z)-5-(tert-butyl)-1-methoxy-3-phenylundec-
MHz, C6D6) δ: 7.48 (d, J = 8.8 Hz, 2H), 7.20 (t, J = 7.6 Hz, 2H),
7.07 (t, J = 6.8 Hz, 1H), 6.54 (d, J = 15.7 Hz, 1H), 5.80 (ddd, J =
4-en-6-yn-2-ol (4ra)
1
Isolated as a 83:17 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.44 (d, 7.8 Hz, 2H), 7.20 (d, J = 8.0 Hz, 2H),
7.06 (td, J = 8.0, 1.2 Hz, 1H), 6.33 (d, J = 9.8 Hz, 1H), 4.37 (dd,
J = 9.6, 5.7 Hz, 1H), 4.17-4.12 (m, 1H), 3.34 (dd, A of ABX, JAB
= 9.3 Hz, JAX = 7.3 Hz, 1H), 3.28 (dd, B of ABX, JAB = 9.3 Hz,
JBX = 3.6 Hz, 1H), 3.02 (s, 3H), 2.28 (s, 1H), 2.21 (t, J = 6.5 Hz,
15.7, 6.0, 0.4 Hz, 1H), 4.27 (bs, 1H), 3.55 (dd, A of ABX, JAB
=
9.8 Hz, JAX = 7.6 Hz, 1H), 3.45 (dd, B of ABX, JAB = 9.8 Hz, JBX
= 3.4 Hz, 1H), 2.44 (t, J = 7.2 Hz, 2H), 2.29 (t, J = 8.0 Hz, 2H),
1.64-1.54 (m, 4H), 1.40-1.29 (m, 4H), 0.91 (s, 9H), 0.87 (t, J =
7.6 Hz, 3H), 0.85 (t, J = 7.6 Hz, 3H), -0.01 (s, 6H); 13C NMR
(101 MHz, C6D6) δ: 208.2, 137.9, 130.2, 129.1, 128.3, 127.4,
126.9, 108.6, 108.0, 73.6, 68.2, 31.0, 30.9, 30.8, 29.8, 26.4, 23.5,
23.3, 18.8, 14.5, 14.5, -4.9; MS (EI, m/z): 371(10), 336(5),
315(20), 296(25), 279(25), 212(20), 168(45), 116(60), 91(55),
75(100), 56(95); FTIR (νmax/cm-1): 3437, 2917, 1451, 1272,
1093, 849, 776, 685. HRMS (ESI) C27H44O2SiNa+ [M+Na]+:
451.3003 (calculated), 451.300 (found).
2H), 1.44-1.31 (m, 4H), 1.22 (s, 9H), 0.82 (t, J = 7.6 Hz, 3H); 13
C
NMR (101 MHz, C6D6) δ: 143.6, 136.1, 131.7, 129.1, 129.0,
127.0, 96.5, 79.5, 75.9, 74.6, 59.0, 50.2, 36.5, 31.7, 29.9, 22.6,
19.8, 14.1; FTIR (νmax/cm-1): 3452, 2958, 2923, 1468, 1354,
1115, 763, 710; MS (EI, m/z): 328(<1, M+), 310(5), 253(25),
197(65), 155(100), 91(40), 57(25).
4.3.37. 1-methoxy-3-(2-(2-phenylhex-1-en-1-
yl)cyclohex-1-en-1-yl)propan-2-one (5sa)
1
4.3.33. (2S,6S,E)-5-cyclohexyl-1-methoxy-7-
(E): H NMR (400 MHz, C6D6) δ: 7.35 (d, J = 7.6 Hz, 2H),
phenylundeca-3,5,6-trien-2-ol (3qa)
7.20-7.16 (m, 2H), 7.11 (d, J = 8.0 Hz, 1H), 6.14 (s, 1H), 3.61(d,
J = 0.8 Hz, 2H), 3.15 (s, 2H), 3.02 (s, 3H), 2.51 (t, J = 7.2 Hz,
2H), 2.08 (d, J = 9.2 Hz, 4H), 1.58 (bs, 4H), 1.35-1.21 (m, 4H),
0.80 (t, J = 6.4 Hz, 3H); 13C NMR (101 MHz, C6D6) δ: 206.0,
142.9, 142.5, 133.5, 129.0, 128.7, 128.3, 128.1, 127.2, 78.0, 59.2,
1
Isolated as a 88:12 mixture of diastereomers; H NMR (400
MHz, C6D6) δ: 7.51 (d, J = 7.4 Hz, 2H), 7.20 (t, J = 7.6 Hz, 2H),
7.07 (t, J = 7.2 Hz, 1H), 6.39 (dd, J = 16.0, 1.2 Hz, 1H), 5.86 (dd,
J = 16.0, 5.9 Hz, 1H), 4.35-4.31 (m, 1H), 3.14 (dd, A of ABX,

45.3, 39.4, 31.1, 30.7, 30.4, 23.6, 23.4, 22.8, 14.4; FTIR (νmax/cm-
1): 2922, 1738, 1440, 1209, 1094, 767, 700; MS (EI, m/z):
326(10, M+): 281(25), 238(95), 181(55), 129(30), 91(100),
45(35).
3. For selected recent examples on the synthesis of allenes, see: a)
ACCEPTED MANUSCRIPT
Yoshida, M.; Ueda, H.; Ihara, M. Tetrahedron Lett. 2005, 46,
6705;
b) Molander, G. A.; Sommers, E. M.; Baker, S. R. J. Org. Chem.
2006, 71, 1563–1568;
c) Miura, T.; Shimada, M.; Ku, S.-Y.; Tamai, T.; Murakami, M.
Angew. Chem. Int. Ed. 2007, 46, 7101–7103;
d) Hayashi, S.; Hirano, K.; Yorimitsu, H.; Oshima, K. J. Am.
Chem. Soc. 2008, 130, 5048–5049;
e) Shu, W.; Jia, G.; Ma, S. Org. Lett. 2009, 11, 117–120;
f) Nishimura, T.; Makino, H.; Nagaosa, M.; Hayashi, T. J. Am.
Chem. Soc. 2010, 132, 12865–12867;
g) Yu, S.; Ma, S. Chem. Commun. 2011, 47, 5384–5418;
h) Wang, Y.; Zhang, W.; Ma, S. J. Am. Chem. Soc. 2013, 135,
11517−11520;
1
(Z): H NMR (400 MHz, C6D6) δ: 7.31 (d, J = 8.0 Hz, 2H),
7.20-7.16 (m, 2H), 7.08-7.03 (m, 1H), 6.12 (s, 1H), 3.67 (d, J =
0.8 Hz, 2H), 3.12 (s, 2H), 3.08 (s, 3H), 2.40 (t, J = 7.2 Hz, 2H),
1.96 (bs, 2H), 1.87 (bs, 2H), 1.48-1.36 (m, 4H), 1.38 (s, 4H), 0.82
(t, J = 6.4 Hz, 3H); 13C NMR (101 MHz, C6D6) δ: 205.8, 143.1,
142.0, 133.5, 129.5, 128.5, 128.0, 127.7, 78.0, 59.2, 45.2, 39.4,
31.3, 31.0, 30.4, 23.7, 23.4, 22.8, 14.4; FTIR (νmax/cm-1): 2922,
1738, 1440, 1209, 1094, 767, 700; MS (EI, m/z): 326(20, M+):
281(25), 238(95), 181(60), 141(35), 91(100), 45(35).
i) Hashimoto, T.; Sakata, K.; Tamakuni, F.; Dutton, M. J.;
Maruoka, K. Nat. Chem. 2013, 5, 240–244;
j) Ye, J.; Ma, S. Org. Chem. Front. 2014, 1, 1210–1224;
k) Wu, S.; Huang, X.; Wu, W.; Li, P.; Fu, C.; Ma, S. Nat.
Commun. 2015, 6, 1-8.
4.3.38. (3aS,7S,7aS,E)-7-((R)-1-hydroxy-2-
methoxyethyl)-5-methyl-2-phenyl-4-(1-
phenylpentylidene)-3a,4,7,7a-tetrahydro-1H-
isoindole-1,3(2H)-dione (6ba)
4. For selected reviews, see: (a) Ma, S. Acc. Chem. Res. 2009, 42,
1679;
1
b) López F.; Mascareñas, J. Chem. Eur. J. 2011, 17, 418–428;
c) Alcaide, B.; Almendros, P. Adv. Synth. Catal., 2011, 353,
2561–2576;
d) Lu, T.; Lu, Z.; Ma, Z.-X.; Zhang, Y.; Hsung, R. P. Chem. Rev.
2013, 113, 4862−4904;
e) Alcaide, B.; Almendros, P. Acc. Chem. Res. 2014, 47, 939–952;
f) Ye, J.; Ma, S. Acc. Chem. Res. 2014, 47, 989–1000;
g) Alcaide, B.; Almendros, P. Eds. Chem. Soc. Rev., 2014, 43,
2879–3206.
Isolated as a 91:9 mixture of diastereomers; H NMR (400
MHz, CDCl3) δ: 7.46-7.42 (m, 3H), 7.37 (t, J = 7.6 Hz, 3H),
7.32-7.29 (m, 2H), 7.15 (d, J = 7.6 Hz, 2H), 6.00 (d, J = 2.4 Hz,
1H), 4.30 (q, J = 5.5 Hz, 1H), 3.93 (d, J = 8.6 Hz, 1H), 3.64-3.56
(m, 2H), 3.41 (s, 3H), 3.14 (dd, J = 8.6, 5.9 Hz, 1H), 2.56-2.48
(m, 1H), 2.40-2.33 (m, 2H), 2.06 (t, J = 1.6 Hz, 3H), 1.34-1.24
(m, 4H), 0.83 (t, J = 7.2 Hz, 3H); 13C NMR (101 MHz, CDCl3) δ:
178.8, 177.0, 143.6, 140.8, 138.4, 131.8, 129.1, 128.8, 128.24,
128.16, 127.3, 126.5, 126.0, 74.8, 69.7, 59.1, 47.1, 44.9, 40.0,
36.0, 30.5, 22.9, 22.2, 13.9; FTIR (νmax/cm-1): 2954, 2849, 1724,
1512, 1367, 1209, 1128, 71; MS (EI, m/z): 441(90), 385(50),
328(40), 237(20), 207(30), 181(100), 145(90), 91(90), 45(35).
HRMS (EI) C29H34NO4 [M+H]+: 460.2482 (calculated); 460.2482
(found).
5. a) Akpınar, G. E.; Kuş, M.; Üçüncü, M.; Karakuş, E.; Artok, L.
Org. Lett. 2011, 13, 748–751;
b) Üçüncü, M.; Karakuş, E.; Kuş, M.; Akpınar, G. E.; Aksın-
Artok, Ö.; Krause, N.; Karaca, N., S. Elmacı, N.; Artok, L. J. Org.
Chem. 2011, 76, 5959–5971;
c) Karagöz, E. Ş.; Kuş, M.; Akpınar, G. E.; Artok, L. J. Org.
Chem. 2014, 79, 9222–9230;
d) Kuş, M.; Artok, L.; Aygün, M. J. Org. Chem. 2015, 80,
5494−5506.
6. We have also disclosed recently that enyne acetates or enyne
oxiranes react with Grignard reagents in the presence of an iron
compound to provide vinylallenes: Aytaç, İ. A; Karatavuk, A. O.;
Kuş, M.; Ziyanak, F.; Artok, L. Asian J. Org. Chem. 2017, 6,
1415–1420.
7. Moriya, T; Miyaura, N.; Suzuki, A. Synlett 1994, 149–151.
8. a) Hirai, A.; Yu, X.-Q.; Tonooka, T.; Miyashita, M. Chem.
Commun. 2003, 2482–2483;
b) Yu, X.-Q.; Hirai, A.; Miyashita, M. Chem. Lett. 2004, 33, 764–
765.
9. Wu, K.-M.; Midland, M. M.; Okamura, W. H. J. Org. Chem.
1990, 55, 4381-4392.
Acknowledgments
The financial support of the Scientific and Technological
Research Council of Turkey and Federal Ministry of Education
and Research (Germany) via the Intensified Cooperation Program
(201T092) is gratefully acknowledged. We thank the Mass
Spectrometry Laboratory of Dortmund University of Technology
and the Environmental Research Centre of Izmir Institute of
Technology for HRMS analyses and GC-MS analyses of a part of
samples.
10. In an our previous report (ref. 5b), the transmetalation step was
proposed to occur from the σ-allenylpalladium complex. However,
the fact that the allylic substitution product 4bf formed as the
major product when the coupling reaction was performed by using
the bulky organoboron 1f (Table 3, entry 5) implies that π-
allylpalladium intermediate (A) should have undergone
transmetalation before the migration of palladium.
11. a) Elsevier, C. J.; Kleijn, H.; Ruitenberg, K.; Vermeer, P. J. Chem.
Soc., Chem. Commun. 1983, 1529–1530;
References and notes
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d) Tsutsumi, K.; Ogoshi, S.; Kakiuchi, K.; Nishiguchi, S.;
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in the presence of Pd/phosphine combination: a) Mikami, K.;
Yoshida, A. Angew. Chem., Int. Ed. Engl. 1997, 36, 858-860;
b) Ogoshi, S.; Nishida, T.; Shinagawa, T.; Kurosawa, H. J. Am.
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h) Pulis, A. P.; Yeung, K.; Procter, D. J. Chem. Sci., 2017, 8,
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1364.

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Tetrahedron
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