Preparation of C 2-symmetric allenes by palladium-catalyzed double-nucleophilic substitution on 3-bromopenta-2,4-dienyl acetate

Article abstract of DOI:10.1021/jo300511e

Easily accessible 3-bromopenta-2,4-dienyl acetate was applied to the palladium-catalyzed reaction with soft nucleophiles. The reaction proceeded through the stepwise 2-fold nucleophilic substitution via formal S _N2′ and S_N2 processes

Full text of DOI:10.1021/jo300511e

Note
pubs.acs.org/joc
Preparation of C2-Symmetric Allenes by Palladium-Catalyzed
Double-Nucleophilic Substitution on 3-Bromopenta-2,4-dienyl
Acetate
Masamichi Ogasawara,* Mayuka Suzuki, and Tamotsu Takahashi*
Catalysis Research Center and Graduate School of Life Science, Hokkaido University, Kita-ku, Sapporo 001-0021, Japan
S
* Supporting Information
ABSTRACT: Easily accessible 3-bromopenta-2,4-dienyl ac-
etate was applied to the palladium-catalyzed reaction with soft
nucleophiles. The reaction proceeded through the stepwise
2-fold nucleophilic substitution via formal SN2′ and SN2 processes giving the various doubly functionalized C2-symmetric allenes
in good yields.
llenes have gained increasing attraction as unique building
blocks in synthetic organic chemistry.1−4 Recently, we
developed a palladium-catalyzed reaction for preparing various
functionalized allenes starting with easily accessible 1-hydro-
carbyl-2-bromo-1,3-dienes (Scheme 1, top).5−8 The reaction
synthesis reaction and the other via a formal SN2-substitution as
with the Tsuji−Trost reaction, to afford various doubly func-
tionalized C2-symmetric allenes in high yields with excellent
regioselectivity. Here we report details of this palladium-
catalyzed double nucleophilic substitution process.
A
Preparation of 3-Bromopenta-2,4-dienyl Acetate (1).
The substrate for this study, 3-bromopenta-2,4-dienyl acetate
(1), was prepared by two routes as shown in Scheme 2.28,29
Scheme 1. Pd-Catalyzed Nucleophilic Substitution on
2-Bromo-1,3-dienes and Allenylmethyl Esters
Scheme 2. Preparation of 3-Bromopenta-2,4-dienyl Acetate
(1)
has been extended to the asymmetric counterparts using an
appropriate chiral palladium catalyst to give the corresponding
axially chiral allenes of high enantiopurity.9−12 The reaction
proceeds via an (alkylidene-π-allyl)palladium intermediate13,14
that is somewhat similar to the widely accepted intermediates
in the Tsuji−Trost reaction.15−18 Alternatively, an analogous
(alkylidene-π-allyl)palladium species can be generated by
oxidative addition of an allenylmethyl ester to a zerovalent
palladium species,19−23 and its reaction with appropriate
nucleophiles also provides comparable allenic products
(Scheme 1, bottom).24−27 Since an allenic CCC moiety
preexists in the allenylmethyl esters, their palladium-catalyzed
nucleophilic substitution is better described as “functionaliza-
tion of allenes” rather than “preparation of allenes”. Never-
theless, the two Pd-catalyzed processes shown in Scheme 1 are
closely related to each other.
In the course of our studies on the Pd-catalyzed reaction of
the bromodienes,5−13 we were interested in examining the
reactivity of 3-bromopenta-2,4-dienyl acetate (1). Compound 1
is a bifunctional molecule and possesses properties and
substructures of both 2-bromo-1,3-dienes and allylic acetates.
Indeed, 1 undergoes the facile 2-fold Pd-catalyzed nucleophilic
substitution, once via a formal SN2′-substition as with our allene
The Pd-catalyzed Stille coupling of 3,3-dibromo-2-propenyl
acetate (2), which was obtained by the Wittig dibromoolefi-
nation of formylmethyl acetate,30,31 with tributylvinyltin gave 1
in 72% yield as an inseparable mixture of the E- and Z-isomers
32−34
1
(E/Z = 10/90 determined by H NMR; Scheme 2 top).
The identity of the minor isomer in 1 ((E)-isomer) was
1
confirmed by GC−MS and H NMR analyses. On the other
hand, the Pd-catalyzed Negishi coupling of TBS-protected
3,3-dibromo-2-propenol 3 with vinylzinc chloride proceeded
with excellent regioselectivity to give (Z)-bromo-diene 4 in
72% yield exclusively.5,28,29,35−40 Deprotection of 4 followed by
acetylation afforded (Z)-1 in 86% yield in isomerically pure
form.
Palladium-Catalyzed Nucleophilic Substitution of 1.
Substrate 1 was subjected to the Pd-catalyzed reaction with
various soft nucleophiles generated from 5a−g and an
Received: March 9, 2012
Published: May 25, 2012
© 2012 American Chemical Society
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The Journal of Organic Chemistry
Note
a
Table 1. Palladium-Catalyzed Synthesis of C2-Symmetric Allenes 6
b
entry
substrate 1
Nu-H 5
base
solvent
temp (°C)
yield of 6 (%)
1
2
3
4
5
6
7
8
(Z)-1
5a
5a
5b
5c
5d
5e
5f
NaH
THF
THF
THF
CH2Cl2
THF
THF
THF
THF
40
40
40
23
23
40
40
23
83 (6a)
87 (6a)
84 (6b)
73 (6c)
81 (6d)
46 (6e)
89 (6f)
67 (6g)
(E/Z)-1
(E/Z)-1
(Z)-1
NaH
tBuOK
tBuOK
tBuOK
NaH
(Z)-1
(E/Z)-1
(E/Z)-1
(Z)-1
NaH
tBuOK
5g
a
The reaction was carried out with 1 (0.50 mmol) and 5 (1.25 mmol) in the given solvent in the presence of an appropriate base and a Pd catalyst
b
(2 mol %) generated from [PdCl(π-allyl)]2 and dpbp. Isolated yield by silica gel chromatography.
Scheme 3. Preparation of Allenic Hydrocarbon 9 by Reductive Desulfonylation of 6f
appropriate base (Table 1). The Pd-catalyzed reaction of (Z)-1
with 5a (2.5 equiv with respect to 1) gave allene 6a in 83%
yield (entry 1). Similarly, the E/Z mixture of 1 afforded 6a in
87% yield under the identical conditions (entry 2). These
results are consistent with our previous reports, which describes
analogous reactivity between (E)- and (Z)-isomers of
1-substituted-2-bromo-1,3-dienes in the Pd-catalyzed reac-
tion.6,13 During the transformation of 1 into 6, the E/Z
isomeric difference in 1 is canceled due to the perpendicular
structure of the allenic CCC moiety in 6, and the
isostructural allene is obtained from either (E)- or (Z)-1. Thus,
the E/Z mixture of 1 can be used for the allene synthesis
without separating the two isomers. Under similar conditions,
the reactions of phenylmalonate 5b (with (E/Z)-1) or
acetamidemalonate 5c (with (Z)-1) provided the corresponding
doubly functionalized allenes 6b or 6c in 84% or 73% yields,
respectively (entries 3 and 4). Triethyl methanetricarboxylate 5d
was also a reactive pronucleophile to give allene 6d in 81% yield
from (Z)-1 in the same way (entry 5). The gem-bis-
(phenylsulfonyl)alkanes such as 5e and 5f could be used as
pronucleophiles in the present transformation,41 and the
corresponding C2-symmetric allenes 6e and 6f were obtained
from (E/Z)-1, respectively (entries 6 and 7). The yield of 6e is
relatively low (46%), although substrate 1 was completely
consumed under the conditions shown in Table 1 (entry 6).
Pronucleophile 5e possesses two active methylene hydrogen
atoms, and it is capable of reacting with 2-fold 1. Thus, the
formation of oligomeric allenes 7, presumably, competed to a
certain extent lowering the yield of monomeric 6e. Indeed, the
reaction using 5f, which has only one acidic methine hydrogen
atom, gave the corresponding C2-symmetric allene (6f) in much
higher yield of 89% (entry 7). This synthetic protocol was
applicable to the reaction with N-pronucleophile 5g as well, and
diaminoallene derivative 6g was isolated in 67% yield by the
reaction between (Z)-1 and 5g (entry 8). The present reaction
is highly regioselective. Except for the formation of 7, the doubly
substituted products are allenes 6 exclusively, and regioisomers
such as 8 were not detected in any cases.
The phenylsulfonyl groups in 6f could be removed by a
treatment with activated magnesium in MeOH/THF according
to the Carpino’s procedure42,43 to give allenic hydrocarbon 9 in
68% yield (Scheme 3). This process can be an efficient method
for preparing symmetric allenic hydrocarbons. Indeed, practical
applicability of the sequential processes was demonstrated by
the experiments on a semimacro scale: 403 mg (1.97 mmol) of
1 afforded 1.68 g (1.79 mmol) of 6f (91% yield), which could
be converted to 9 (451 mg) in 67% yield.
The C2-symmetric allenes 6 are axially chiral, and application
of an appropriate chiral palladium species to the reaction may
furnish allenes 6 in enantiomerically enriched forms.3,9−12 The
asymmetric extension was explored for a reaction of 1 with 5c,
and the results are shown in Scheme 4. The asymmetric
reaction catalyzed by a palladium species generated from
Pd(dba)2 and (R)-segphos44 proceeded with excellent enantio-
selectivity at 23 °C, and (−)-6c of 96% ee was obtained in
44% yield using CsOtBu as a base.9 The yield of (−)-6c could
be increased to 70% at 40 °C; however, the enantioselectivity
was diminished to 81% ee. The absolute configuration of
levorotatory (−)-6c was deduced to be (R) by the Lowe−
Brewster rule.45,46
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Note
Scheme 4. Palladium-Catalyzed Asymmetric Synthesis of Axially Chiral Allene (R)-(−)-6c
Consideration to Reaction Pathways from 1 to 6.
Substrate 1 possesses two different sites susceptible to
activation with palladium catalysis, and thus, there are two
possible reaction pathways from 1 to 6 (Scheme 5). Treatment
EXPERIMENTAL SECTION
■
General Methods. All anaerobic and/or moisture-sensitive
manipulations were carried out with standard Schlenk techniques
under predried nitrogen or with glovebox techniques under prepurified
argon. 1H NMR (at 400 MHz) and 13C NMR (at 101 MHz) chemical
shifts are reported in ppm downfield of internal tetramethylsilane.
31P NMR (at 162 MHz) chemical shifts are externally referenced to
85% H3PO4. Tetrahydrofuran and benzene were distilled from
benzophenone−ketyl under nitrogen prior to use. Dichloromethane
was distilled from CaH2 under nitrogen prior to use. Acetoxyace-
taldehyde,49 (Z)-TBS-protected diene 4,28 dpbp,50 and (R)-segphos44
were prepared as reported. All other chemicals were obtained from
commercial sources and used without additional purification.
Scheme 5. Possible Reaction Pathways from 1 to 6
3,3-Dibromo-2-propenyl Acetate (2). This compound was
prepared by the reported method with minor modifications. To a
CH2Cl2 (250 mL) solution of CBr4 (35.2 g, 106 mmol) was added
PPh3 (55.7 g, 212 mmol) portionwise at 0 °C, and the solution was
allowed to stir at this temperature for 30 min. Acetoxyacetaldehyde
(5.42 g, 53.1 mmol) was added to the solution at 0 °C, and the
mixture was stirred at the same temperature for 30 min. After the reac-
tion mixture was quenched with a small amount of water (ca. 2 mL),
the mixture was concentrated under reduced pressure. Addition of
hexane (ca. 500 mL) to the concentrated solution precipitated
triphenylphosphine oxide as pale yellow solid, which was removed by
filtration. The filtrate was evaporated, and the residual oil was purified
by column chromatography on silica gel (with hexane/ethyl acetate =
5/1) followed by vacuum transfer to give the title compound (7.16 g,
52% yield) as a colorless oil. 1H NMR (CDCl3): δ 2.08 (s, 3 H), 4.56
(d, J = 6.3 Hz, 2H), 6.61 (t, J = 6.3 Hz, 1H). 13C NMR (CDCl3):
δ 20.7, 63.8, 94.1, 132.7, 170.6. EI-HRMS: calcd for C5H6Br2O2
255.8735, found 255.8738.
of 1 with an equimolar mixture of 5a and NaH (1 equiv with
respect to 1) in THF in the presence of the Pd/dpbp catalyst
(2 mol %) did not afford either 10 or 11, but the reac-
tion mixture contained unreacted 1 and 6a both in ca. 50%
yields. Apparently, monosubstituted intermediates 10 and/or 11
are more reactive than 1 under the present reaction conditions.
Pd-catalyzed reactions of compounds having an 1-acetoxy-3-
bromo-2-propene substructure, which is a substructure shown
in 1, were examined by de Meijere47 and Organ.48 They
showed that the vinylic bromo substituents deactivated the
allylic acetate moieties toward ionization in the presence of the
Pd catalyst. Thus, oxidative addition of Pd(0) to the vinylic
C−Br takes place preferentially to ionization at the allylic
acetate. Because of the close structural similarity between their
substrates and 1, we propose that the route via 10 is the most
likely pathway from 1 to 6 in the present reaction. The
deactivating group (vinylic Br) is eliminated during the first
Pd-catalyzed process, and thus, monosubstituted intermediate
10 reacts faster than 1 to furnish 6 even in the presence of
remaining 1. Although this explanation is consistent with the
experimental observations, a possibility involving the both
pathways cannot be ruled out assuming that both 10 and 11 are
more reactive than 1 under the Pd catalysis.
3-Bromo-2,4-pentadienyl Acetate (1). To a toluene (125 mL)
solution of Pd2(dba)3·CHCl3 (325 mg, 0.63 mmol), tri-2-furylphos-
n
phine (874 mg, 3.76 mmol), and Bu3Sn(vinyl) (7.99 g, 25.1 mmol)
was added 2 (6.48 g, 25.1 mmol) at room temperature, and the
solution was stirred at 60 °C until complete consumption of 2
(checked by GC). The mixture was filtered through a short pad of
silica gel. After the solvents were removed under reduced pressure, the
residue was purified by column chromatography on silica gel (with
hexane/ethyl acetate = 95/5) followed by vacuum transfer to give the
isomeric mixture of 1 (4.10 g, 72% yield) as a pale yellow oil. The E/Z
ratio in 1 was determined to be 10/90 by 1H NMR analysis. (Z)-1: 1H
NMR (CDCl3) δ 2.09 (s, 3H), 4.84 (d, J = 6.0 Hz, 2H), 5.32 (d, J =
10.5 Hz, 1H), 5.66 (d, J = 16.3 Hz, 1H), 6.14 (t, J = 6.0 Hz, 1H), 6.34
(dd, J = 16.3 and 10.5 Hz, 1H); 13C NMR (CDCl3) δ 20.8, 63.8,
120.1, 128.0, 128.1, 134.9, 170.7. (E)-1: 1H NMR (CDCl3): δ 2.08 (s,
3H), 4.70 (d, J = 7.7 Hz, 2H), 5.46 (d, J = 10.6 Hz, 1H), 5.74 (d, J =
16.1 Hz, 1H), 6.21 (t, J = 7.7 Hz, 1H), 6.61 (dd, J = 16.1 and 10.6 Hz,
1H); EI-HRMS calcd for C7H9BrO2 203.9786, found 203.9789.
1,1-Bis(phenylsulfonyl)undecane (5d). To a suspension of NaH
[1.1 equiv with respect to (PhSO2)2CH2] in dry DMF (3 mL/mmol)
was added solid (PhSO2)2CH2. After hydrogen evolution had ceased,
1-iododecane [1.2 equiv with respect to (PhSO2)2CH2] was added,
and the reaction mixture was stirred at 80 °C overnight. The reaction
In summary, we have demonstrated that 3-bromopenta-2,4-
dienyl acetate 1 is an excellent precursor to a variety of doubly
functionalized C2-symmetric allenes. The reaction is effectively
catalyzed by the Pd/dpbp complex, and 1 undergoes the 2-fold
nucleophilic substitution via formal SN2′ and SN2 processes to
give the allenic products in high yields.
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The Journal of Organic Chemistry
Note
mixture was concentrated under reduced pressure. The residue was
dissolved in CH2Cl2, and filtered through a short pad of silica gel.
Concentration followed by recrystallization from hot MeOH afforded
the pure product: 1H NMR (CDCl3) δ 0.89 (t, J = 7.1 Hz. 3H), 1.19−
1.32 (br, 14H), 1.52−1.57 (m, 2H), 2.11−2.15 (m, 2H), 4.37 (t, J =
5.7 Hz. 1H), 7.57−7.60 (m, 4H), 7.68−7.73 (m, 2H), 7.95−7.98 (m,
4H); 13C NMR (CDCl3) δ 14.2, 22.7, 25.7, 28.2, 28.97, 29.04, 29.3,
29.4, 29.5, 31.9, 83.8, 129.1, 129.7, 134.6, 137.9. Anal. Calcd for
C23H32O4S2: C, 63.27; H, 7.39. Found: C, 63.23; H, 7.35. A molecular
ion peak was not detected in a HRMS spectrum for this compound.
Palladium-Catalyzed Synthesis of Allenes 6. Preparation of
allenes 6 was conducted according to a reported procedure1 with slight
modifications. The reaction conditions and the results are summarized
in Table 1. A mixture of [PdCl(π-allyl)]2 (1.8 mg, 10 μmol/Pd), dpbp
(5.7 mg, 11 μmol), and 1 (0.50 mmol) was dissolved in an appropriate
solvent (5 mL), and the solution was added to a mixture of 5
(1.25 mmol) and base (1.25 mmol) via cannula under nitrogen. The
mixture was stirred for 12 h and then filtered through a short pad of
silica gel to remove precipitated inorganic salts. The silica gel pad was
washed with a small amount of Et2O three times, and the combined
solution was evaporated to dryness under reduced pressure. The
yellow residue was chromatographed on silica gel to give allene 6 in
pure form. The characterization data of allenic products 6 are listed
below.
521.2839, found 521.2833. Anal. Calcd for C25H42O8N2: C, 60.22; H,
8.49; N, 5.62. Found: C, 59.97; H, 8.44; N, 5.44.
Pd-Catalyzed Asymmetric Synthesis of (R)-(−)-6c. To a
mixture of Pd(dba)2 (7.0 mg, 12 μmol), (R)-segphos (8.2 mg,
13 μmol), 5c (159 mg, 732 μmol), and CsOtBu (126 mg, 612 μmol)
in THF (3 mL) was added 1 (51.0 mg, 249 μmol) by means of syringe
under nitrogen. After being stirred for 24 h at 23 °C, the mixture
was filtered through a short pad of Al2O3 to remove precipitated
inorganic salts. The Al2O3 pad was washed with a small amount of a
hexane/EtOAc (1:1) mixture, and the combined organic solution
was evaporated to dryness under reduced pressure. The residue was
purified by chromatography on Al2O3 to give (R)-(−)-6c in pure form.
Yield: 54.0 mg (44%). The enantiopurity of (R)-(−)-6c was
determined to be 96% ee by chiral HPLC analysis. The absolute
configuration was deduced to be (R) by the Lowe−Brewster rule45,46
from the sign of optical rotation. (R)-(−)-6c: [α]21 = −51.8 (c 0.49,
D
CHCl3 for the sample of 96% ee). Chiral HPLC analysis conditions:
Chiralpak AD-H; eluent, hexane/iPrOH = 4/1; flow rate, 0.8 mL/min;
t1 [(S)-enantiomer] = 19.6 min, t2 [(R)-enantiomer] = 21.4 min.
13,14-Heptacosadiene (9). Magnesium turnings (228 mg,
9.38 mmol) were placed in a Schlenk flask under nitrogen, and to
this were added MeOH (5 mL) and a THF (1 mL) solution of 6d
(294 mg, 314 μmol) via syringe. The mixture was stirred at room tem-
perature for 3 h. The reaction mixture was quenched with saturated
aqueous NH4Cl and extracted with ether three times. The combined
organic solution was dried over MgSO4 and evaporated under reduced
pressure. The residue was purified by chromatography on silica gel
(with hexane) to give 9 (80.0 mg, 68% yield) as a colorless oil:
1H NMR (CDCl3) δ 0.88 (t, J = 6.9 Hz, 6H), 1.26−1.41 (m, 40H),
1.94−1.98 (m, 4H), 5.03−5.08 (m, 2H); 13C NMR (CDCl3) δ 14.2,
22.8, 29.1, 29.2, 29.3, 29.4, 29.6, 29.736, 29.743, 29.76, 29.78, 32.0,
91.0, 203.9; EI-HRMS calcd for C27H52 376.4069, found 376.4054.
Tetramethyl 4,5-nonadiene-2,2,8,8-tetracarboxylate (6a): 1H
NMR (CDCl3) δ 1.43 (s, 6H), 2.52−2.56 (m, 4H), 3.72 (s, 12H),
4.94−5.00 (m, 2H); 13C NMR (CDCl3) δ 19.9, 35.8, 52.59, 52.65,
53.9, 85.3, 172.1, 172.2, 207.8; EI-HRMS calcd for C17H24O8
356.1471, found 356.1469. Anal. Calcd for C17H24O8: C, 57.30; H,
6.79. Found: C, 57.12; H, 6.78.
Tetraethyl 1,7-diphenyl-3,4-heptadiene-1,1,7,7-tetracarbox-
ylate (6b): 1H NMR (CDCl3) δ 1.23 (t, J = 7.1 Hz, 12H), 2.83−2.95
(m, 4H), 4.15−4.26 (m, 8H), 4.90−4.95 (m, 2H), 7.25−7.36 (m,
10H); 13CNMR (CDCl3): δ 14.1 (unresolved −CO2CH2CH3), 35.7,
61.68, 61.71, 62.8, 85.8, 127.6, 128.1, 128.3, 136.5, 170.2, 170.3, 207.6;
ESI-HRMS calcd for C31H36O8 536.2410, found 536.2405. Anal. Calcd
for C31H36O8: C, 69.39; H, 6.76. Found: C, 69.89; H, 6.79.
Tetraethyl 1,7-diacetamido-3,4-heptadiene-1,1,7,7-tetracar-
boxylate (6c): 1H NMR (CDCl3) δ 1.26 (t, J = 7.1 Hz, 12H), 2.05 (s,
6H), 2.97−3.00 (m, 4H), 4.21−4.29(m, 8H), 4.81−4.86(m, 2H),
6.80(s, 2H); 13CNMR (CDCl3): δ 13.96, 13.97, 22.9, 32.5, 62.61,
62.65, 66.2, 84.2, 167.4, 167.5, 169.1, 207.9; ESI-HRMS calcd for
C23H34O10N2Na (M + Na) 521.2111, found 521.2106. Anal. Calcd
for C23H34O10N2: C, 55.41; H, 6.87; N, 5.62. Found: C, 55.34; H,
6.83; N, 5.37.
ASSOCIATED CONTENT
■
S
* Supporting Information
1H and 13C NMR spectra for all the new compounds and chiral
HPLC chromatograms of 6c. This material is available free of
charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: ogasawar@cat.hokudai.ac.jp, tamotsu@cat.hokudai.ac.
jp.
Hexaethyl 3,4-heptadiene-1,1,1,7,7,7-hexacarboxylate (6d):
Notes
1H NMR (CDCl3) δ 1.28 (t, J = 7.1 Hz, 18H), 2.74−2.88 (m, 4H),
The authors declare no competing financial interest.
2.97−3.00 (q, J = 7.1 Hz, 12H), 5.29−5.34(m, 2H); 13CNMR
(CDCl3) δ 13.9, 33.1, 62.2, 65.7, 85.7, 166.5, 207.6; EI-HRMS calcd
for C25H36O12 528.2207, found 528.2195. Anal. Calcd for C25H36O12:
C, 56.81; H, 6.87. Found: C, 56.63; H, 6.86.
ACKNOWLEDGMENTS
■
This work was supported by a Grant-in-Aid for Scientific
Research (B) (24350044) to M.O. from MEXT, Japan.
1,1,7,7-Tetrakis(phenylsulfonyl)-3,4-heptadiene (6e): 1H
NMR (CDCl3) δ 2.90 (dd, J = 7.8 and 5.9 Hz, 4H), 4.75 (t, J = 5.9
Hz, 2H), 5.30−5.35 (m, 2H), 7.51−7.56 (m, 8H), 7.64−7.70 (m, 4H),
7.90−7.97 (m, 8H); 13C NMR (CDCl3) δ 24.7, 82.4, 90.2, 129.26,
129.27, 129.6, 129.9, 134.7, 134.8, 137.7, 138.1, 204.8; ESI-HRMS
calcd for C31H28O8S4Na (M + Na) 679.0565, found 679.0563.
11,11,17,17-Tetrakis(phenylsulfonyl)-13,14-heptacosadiene
REFERENCES
■
(1) Yu, S.; Ma, S. Angew. Chem., Int. Ed. 2012, 51, 3074.
(2) Yu, S.; Ma, S. Chem. Commun. 2011, 47, 5384.
(3) Ogasawara, M. Tetrahedron: Asymmetry 2009, 20, 259.
(4) Krause, N., Hashmi, A. S. K., Eds. Modern Allene Chemistry;
Wiley-VCH: Weinheim, 2004.
1
(6f): H NMR (CDCl3) δ 0.88 (t, J = 7.2 Hz, 6H), 1.25 (br, 28H),
1.61−1.71 (m, 4H), 2.16−2.18 (m, 4H), 2.96−3.10 (m, 4H), 5.50−
5.55 (m, 2H), 7.57−7.61 (m, 8H), 7.69−7.72 (m, 4H), 8.05−8.07
(m, 8H); 13C NMR (CDCl3) δ 14.2, 22.8, 23.5, 28.5, 29.1, 29.38,
29.41, 29.6, 29.7, 30.4, 32.0, 85.6, 91.2, 128.7, 128.8, 131.3, 131.4,
134.7 (unresolved two diastereotopic signals), 136.9 (unresolved two
diastereotopic signals), 207.4; ESI-HRMS calcd for C51H68O8S4Na
(M + Na) 959.3695, found 959.3698.
(5) Ogasawara, M.; Ikeda, H.; Hayashi, T. Angew. Chem., Int. Ed.
2000, 39, 1042.
(6) Ogasawara, M.; Ge, Y.; Uetake, K.; Fan, L.; Takahashi, T. J. Org.
Chem. 2005, 70, 3871.
(7) Ogasawara, M.; Okada, A.; Nakajima, K.; Takahashi, T. Org. Lett.
2009, 11, 177.
(8) Ogasawara, M.; Murakami, H.; Furukawa, T.; Takahashi, T.;
Shibata, N. Chem. Commun. 2009, 7366.
(9) Ogasawara, M.; Ikeda, H.; Nagano, T.; Hayashi, T. J. Am. Chem.
N,N,N′,N′-Tetrakis(tert-butoxycarbonyl)-2,3-pentadiene-1,5-
1
diamine (6g): H NMR (CDCl3) δ 1.48 (s, 36H), 4.08−4.21 (m,
4H), 5.25−5.30 (m, 2H); 13C NMR (CDCl3) δ 28.1, 45.2, 82.4,
89.5, 152.1, 205.2; ESI-HRMS calcd for C25H42O8N2Na (M + Na)
Soc. 2001, 123, 2089.
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The Journal of Organic Chemistry
Note
(10) Ogasawara, M.; Ueyama, K.; Nagano, T.; Mizuhata, Y.; Hayashi,
T. Org. Lett. 2003, 5, 217.
(11) Ogasawara, M.; Nagano, T.; Hayashi, T. J. Org. Chem. 2005, 70,
5764.
(12) Ogasawara, M.; Okada, A.; Subbarayan, V.; Sorgel, S.;
̈
Takahashi, T. Org. Lett. 2010, 12, 5736.
(13) Ogasawara, M.; Okada, A.; Watanabe, S.; Fan, L.; Uetake, K.;
Nakajima, K.; Takahashi, T. Organometallics 2007, 26, 5025.
(14) Zeng, X.; Hu, Q.; Qian, M.; Negishi, E. J. Am. Chem. Soc. 2003,
125, 13636.
(15) Tsuji, J. Acc. Chem. Res. 1969, 2, 144.
(16) Trost, B. M.; Van Vranken, D. L. Chem. Rev. 1996, 96, 395.
(17) Trost, B. M.; Chulbom, L. In Catalytic Asymmetric Synthesis, 2nd
ed.; Ojima, I., Ed.; VCH: New York, 2000; p 593.
(18) Consiglio, G.; Waymouth, M. Chem. Rev. 1989, 89, 257.
(19) Benyunes, S. A.; Brandt, L.; Fries, A.; Green, M.; Mahon, M. F.;
Papworth, T. M. T. J. Chem. Soc., Dalton Trans. 1993, 3785.
(20) Kleijn, H.; Westmijze, H.; Meijer, J.; Vermeer, P. Recl. Trav.
Chim. Pays-Bas 1983, 102, 378.
́
(21) Djahanbini, D.; Cazes, B.; Gore, J. Tetrahedron 1985, 41, 867.
(22) Nokami, J.; Maihara, A.; Tsuji, J. Tetrahedron Lett. 1990, 31,
5629.
(23) Piotti, M. E.; Alper, H. J. Org. Chem. 1994, 59, 1956.
(24) Djahanbini, D.; Cazes, B.; Gore,
203.
́
J. Tetrahedron Lett. 1984, 25,
(25) Trost, B. M.; Tour, J. M. J. Org. Chem. 1989, 54, 484.
(26) Imada, Y.; Ueno, K.; Kutsuwa, K.; Murahashi, S. Chem. Lett.
2002, 140.
(27) Trost, B. M.; Fandrick, D. R.; Dinh, D. C. J. Am. Chem. Soc.
2005, 127, 14186.
(28) Cayzer, T. N.; Wong, L. S.-M.; Turner, P.; Paddon-Row, M. N.;
Sherburn, M. S. Chem.Eur. J. 2002, 8, 739.
(29) Miller, N. A.; Willis, A. C.; Sherburn, M. S. Chem. Commun.
2008, 1226.
(30) Ramirez, F.; Desai, N. B.; McKelvie, N. J. Am. Chem. Soc. 1962,
84, 1745.
(31) Corey, E. J.; Fuchs, P. L. Tetrahedron Lett. 1972, 36, 3769.
(32) Uenishi, J.; Kawahama, R.; Yonemitsu, O.; Tsuji, J. J. Org. Chem.
1996, 61, 5716.
(33) Uenishi, J.; Kawahama, R.; Shiga, Y.; Yonemitsu, O.; Tsuji, J.
Tetrahedron Lett. 1996, 37, 6759.
(34) Shen, W.; Wang., L. J. Org. Chem. 1999, 64, 8873.
(35) Xu, C.; Negishi, E. Tetrahedron Lett. 1999, 40, 431.
(36) Ogasawara, M.; Ikeda, H.; Ohtsuki, K.; Hayashi, T. Chem. Lett.
2000, 776.
(37) Shi, J.; Negishi, E. J. Organomet. Chem. 2003, 687, 518.
(38) Minato, A.; Suzuki, K.; Tamao, K. J. Am. Chem. Soc. 1987, 109,
1257.
(39) Roush, W. R.; Moriarty, K. J.; Brown, B. B. Tetrahedron Lett.
1990, 31, 6509.
(40) Minato, A. J. Org. Chem. 1991, 56, 4052.
(41) Trost, B. M.; Verhoeven, T. R.; Fortunak, J. M. Tetrahedron Lett.
1979, 20, 2301.
(42) Brown, A. C.; Carpino, L. A. J. Org. Chem. 1985, 50, 1749.
́
(43) Najera, C.; Yus, M. Tetrahedron 1999, 55, 10547.
(44) Saito, T.; Yokozawa, T.; Ishizaki, T.; Moroi, T.; Sayo, N.; Miura,
T.; Kumobayashi, H. Adv. Synth. Catal. 2001, 343, 264.
(45) Lowe, G. Chem. Commun. 1965, 411.
(46) Brewster, J. H. Top. Stereochem. 1967, 2, 1.
(47) Steinig, A. G.; de Meijere, A. Eur. J. Org. Chem. 1999, 1333.
(48) Comer, E.; Organ, M. G.; Hynes, S. J. J. Am. Chem. Soc. 2004,
126, 16087.
(49) Nagasawa, J.; Araki, Y.; Ishido, Y. J. Org. Chem. 1981, 46, 1734.
(50) dpbp = 2,2′-bis(diphenylphosphino)-1,1′-biphenyl. See:
Ogasawara, M.; Yoshida, K.; Hayashi, T. Organometallics 2000, 19,
1567 and references cited therein.
5410
dx.doi.org/10.1021/jo300511e | J. Org. Chem. 2012, 77, 5406−5410