Trans-Selective Olefination of Carbonyl Compounds by Low-Valent Titanium-Mediated Dehydroxybenzotriazolylation

Article abstract of DOI:10.1021/jo980616v

Lithiation with n-butyllithium of a variety of benzotriazole derivatives 1a-f and 5a-d, all containing a proton α to the benzotriazolyl moiety, gave anions which underwent addition to aliphatic, aromatic, and α,β-unsaturated aldehydes and cyclic and acyclic ketones. The resultant N-(β-hydroxyalkyl)benzotriazole derivatives 3a-m, 6a-g, 9a-d, and 10a were dehydroxybenzotriazolylated when treated with low-valent titanium to give alkenes 4a-m, dienes 7a- j, and triene 11a, with selectivity for the trans isomers without separation of diastereoisomeric intermediates. This method offers an alternative to the three most frequently used methods for the formation of alkenes from carbonyl compounds-the Wittig, Peterson, and Julia reactions-especially in the formation of tri- and tetrasubstituted alkenes.

Full text of DOI:10.1021/jo980616v

6704
J . Org. Chem. 1998, 63, 6704-6709
Tr a n s-Selective Olefin a tion of Ca r bon yl Com p ou n d s by
Low -Va len t Tita n iu m -Med ia ted Deh yd r oxyben zotr ia zolyla tion
Alan R. Katritzky,* Dai Cheng, Scott A. Henderson, and J ianqing Li
Center for Heterocyclic Compounds, Department of Chemistry, University of Florida,
Gainesville, Florida 32611-7200
Received April 3, 1998
Lithiation with n-butyllithium of a variety of benzotriazole derivatives 1a -f and 5a -d , all
containing a proton R to the benzotriazolyl moiety, gave anions which underwent addition to
aliphatic, aromatic, and R,â-unsaturated aldehydes and cyclic and acyclic ketones. The resultant
N-(â-hydroxyalkyl)benzotriazole derivatives 3a -m , 6a -g, 9a -d , and 10a were dehydroxybenzo-
triazolylated when treated with low-valent titanium to give alkenes 4a -m , dienes 7a -j, and triene
11a , with selectivity for the trans isomers without separation of diastereoisomeric intermediates.
This method offers an alternative to the three most frequently used methods for the formation of
alkenes from carbonyl compoundssthe Wittig, Peterson, and J ulia reactionssespecially in the
formation of tri- and tetrasubstituted alkenes.
Sch em e 1
In tr od u ction
Constructive olefination of carbonyl compounds is a
fundamental transformation in organic synthesis. Wit-
tig, Peterson, and J ulia reactions are the three most
frequently used methods.1a-c The stereochemical pro-
cesses of the Wittig reactions are sensitive to the reaction
conditions (solvents, temperatures, bases, additives, etc.),
which frequently neccessitates individual tuning of the
reaction conditions, depending on the specific structures
of the carbonyl compound and the ylide, to obtain good
carbon-carbon double bond stereoselectivity.1b Such
tuning generally succeeds both for highly reactive ylides
and for stable ylides, but for ylides with intermediate
reactivity (e.g., benzylic and allylic ylides) the results can
be unsatisfactory.1b The Peterson reaction2 can provide
stereospecific control for either trans or cis isomers
depending on the reaction conditions but this variant
requires the separation of the diastereomeric intermedi-
ates.3 Difficulty in the preparation of R-silyl carbanions
usually limits the Peterson reaction to the synthesis of
methylene derivatives.1b,4 The original procedure for the
J ulia reaction5swhich is lengthy and employs mercury
reagentsspresents difficulties in the preparation of
trisubstituted alkenes. An improved J ulia coupling
reaction using benzothiazolyl sulfones6 gives excellent
stereoselectivity for aliphatic derivatives, but it is less
predictable for allylic and benzylic benzothiazolyl sul-
fones.7a-c
During the past two decades, low-valent titanium-
induced coupling of carbonyl compounds has received
wide application in intramolecular cyclizations, but the
unsymmetrical intermolecular variant generally suffers
from statistical crossovers.8a-b Recently, unsymmetric
intermolecular coupling between carbonyl compounds
and dithioacetals under low-valent titanium conditions
has been reported, but the products generally showed
little cis/trans stereoselectivity.9
Our preliminary communication10 disclosed that low-
valent titanium enabled an effective dehydroxybenzo-
triazolylation synthesis of olefins and dienes with ste-
reoselectivity for the trans isomers, which constitutes an
alternative to the J ulia reaction. This was the first report
of reductive elimination of two different heteroatoms R
to each other using low-valent titanium to synthesize
olefins. More recently we have applied this method to
(1) (a) Maguire, A. R. In Comprehensive Organic Functional Group
Transformations; Katritzky, A. R., Meth-Cohn, O., Rees, C. W., Eds.;
Pergamon: New York, 1995; Vol. 1, p 589. (b) Gosney, I.; Lloyd, D. In
Comprehensive Organic Functional Group Transformations; Katritzky,
A. R., Meth-Cohn, O., Rees, C. W., Eds.; Pergamon: New York, 1995;
Vol. 1, p 719. (c) Kelly, S. E. In Comprehensive Organic Synthesis;
Trost, B. M., Ed.; Pergamon: New York, 1991; Vol. 1, p 729.
(2) Peterson, D. J . J . Org. Chem. 1968, 33, 780.
(3) Hudrlik, P. F.; Peterson, D. J . Am. Chem. Soc. 1975, 97, 1464.
(4) Katritzky, A. R.; Toader, D. J . Am. Chem. Soc. 1997, 119, 9321.
(5) J ulia, M.; Paris, J .-M. Tetrahedron Lett. 1973, 4833.
(6) Baudin, J . B.; Hareau, G.; J ulia, S. A.; Ruel, O. Tetrahedron Lett.
1991, 32, 1175.
(7) (a) Baudin, J . B.; Hareau, G.; J ulia, S. A.; Ruel, O. Bull. Soc.
Chim. Fr. 1993, 130, 336. (b) Baudin, J . B.; Hareau, G.; J ulia, S. A.;
Lorne, R.; Ruel, O. Bull. Soc. Chim. Fr. 1993, 130, 856. (c) Bellingham,
R.; J arowicki, K.; Kocienski, P.; Martin, V. Synthesis 1996, 285.
(8) (a) McMurry, J . E. Chem. Rev. 1989, 89, 1513. (b) Fu¨rstner, A.;
Bogdanovic, B. Angew. Chem., Int. Ed. Engl. 1996, 35, 2442.
(9) Horikawa, Y.; Watanabe, M.; Fujiwara, T.; Takeda, T. J . Am.
Chem. Soc. 1997, 119, 1127.
(10) Katritzky, A. R.; Li, J . J . Org. Chem. 1997, 62, 238.
S0022-3263(98)00616-1 CCC: $15.00 © 1998 American Chemical Society
Published on Web 09/02/1998

Trans-Selective Olefination of CO Compounds
J . Org. Chem., Vol. 63, No. 19, 1998 6705
Sch em e 2
pounds 5c,d were obtained by the reaction of benzotria-
zole with the corresponding allyl halide in the presence
of sodium hydroxide in ethanol by analogy to the litera-
ture.18 The preparation and characterization of com-
pound 1d is described in the Experimental Section.
P r ep a r a tion of 1-(â-Hyd r oxya lk yl)ben zotr ia zoles
3a -m , 6a -g, 9a -d , a n d 10a . Deprotonation of com-
pounds 1a -h and 5a -d with n-butyllithium gave dark
colored solutions of the corresponding anions which
underwent nucleophilic addition to the carbonyl com-
pounds 2a -n and 8a -c to form the hydroxy intermedi-
ates 3a -m , 6a -g, 9a -d , and 10a as diastereomeric
mixtures. These reactions generally proceeded quickly
at -78 °C accompanied by the disappearance of the dark
color. Exceptionally, the preparation of 3k ,l was carried
1
out at elevated temperatures. The H NMR spectra of
the hydroxy intermediates after workup indicated that
the formation of 3a ,e-g,i-j, 6a -b, and 9h were virtually
quantitative. Intermediate 3k was not quantitative even
if heated to 60 °C, while for 3h about 20% starting
material was recovered presumably because of proton
exchange between carbonyl compound 2h and lithiated
1d . Proton exchange between lithiated 1d and tetralone
2j simply overwhelmed the desired nucleophilic addition
under standard conditions. As the reductive elimination
mechanism leading to trans olefinations is believed to
involve the rotation of the radical or anionic intermedi-
ates11 similar to McMurry and J ulia reactions,1a-c,8a no
effort has been made to systematically study the ratios
of the two possible diastereomers of 3a -m , 6a -g, 9a -
d , and 10a . We previously showed10 that separation of
the diastereomeric mixtures was not needed and there-
fore the crude reaction mixtures 3a -m , 6a -g, 9a -d , and
10a were used directly for the reductive-elimination
reaction.
Sch em e 3
Rea gen ts in Gen er a tin g th e Low -Va len t Tita -
n iu m R ea ct ion Med ia . In the initial communicated
work, TiCl3/Li was employed to generate the low-valent
titanium.10 We soon found11 that TiCl3/Li sometimes
gave unsatisfactory yields of olefins 4. By using Zn-Cu
couple (method C) as the reductive metal, the yields were
generally improved,11 which is in accordance with the
literature.8a We have now also adjusted this olefination
method to utilize the more readily available TiCl4 (method
E) due to recurring difficulties in obtaining TiCl3 from
commercial sources. The addition of tertiary amines has
been recommended to increase the yields for McMurry
coupling;8a,19 therefore we attempted most of the dehy-
droxybenzotriazolylations in the presence of triethyl-
amine (methods D and E). The number of methods
reflects an evolution in the method of LVT preparation.
As TiCl3 is no longer commercially available, method E
is our method of choice.
the synthesis of chiral allylamines for R-amino acid
esters.11 Our previous work had been confined to ben-
zylic and allylic substrates. We now report a more
extensive study covering a variety of benzotriazole de-
rivatives 1a -h and 5a -d sincluding those containing
heteroaryl groups (1e-f,h ) and tertiary starting material
(1d )sto form olefins (Scheme 1) and of allylic benzotria-
zole compounds 5a -d to form dienes (Scheme 2). The
use of R,â-unsaturated carbonyl compounds 8a -c with
benzotriazole derivatives 1a ,d ,g-h also leads to the
formation of dienes (Scheme 2). The combination of the
allylic benzotriazole 5b with R,â-unsaturated carbonyl
compound 8b gave the triene 11a (Scheme 3). We also
discuss alternative methods for generating the low-valent
titanium reagent.
2-P yr id yl System s. Difficulties in performing reduc-
tive olefination under low-valent titanium conditions for
2-pyridyl aryl ketones were reported by Newkome et al.
and attributed to the formation of five-membered ring
complexes.20 The addition of triethylamine prevents the
formation of the five-membered ring complexes, and
olefinations of the 2-pyridyl system were achieved under
Resu lts a n d Discu ssion
P r ep a r a t ion of t h e St a r t in g Ma t er ia ls. Com-
pounds 1a ,b,12 1c,13 1e,14 1f,15 1g,16 1h ,17 5a ,18 and 5b17
were prepared by the literature methods quoted. Com-
(11) Katritzky, A. R.; Cheng, D.; Li. J . J . Org. Chem. 1998, 63, 3438.
(12) Gibson, M. S. J . Chem. Soc. 1956, 1056.
(13) Katritzky, A. R.; Gordeev, M. F.; Greenhill, J . V.; Steel, P. J . J .
Chem. Soc., Perkin Trans. 1 1992, 1111.
(14) Katritzky, A. R.; Xie, L.; Cundy, D. Synth. Commun. 1995, 25,
539.
(15) Katritzky, A. R.; Yao, G.; Rachwal, S. J . Heterocycl. Chem. 1994,
31, 757.
(16) Katritzky, A. R.; Lan, X.; Lam, J . N. Synthesis 1990, 341.
(17) Katritzky, A. R.; Xie, L.; Toader, D.; Serdyuk, L. J . Am. Chem.
Soc. 1995, 117, 12015.
(18) Katritzky, A. R.; Li, J .; Malhotra, N. Liebigs Ann. Chem. 1992,
843.
(19) McMurry, J . E.; Miller, D. D. J . Am. Chem. Soc. 1983, 105, 1660.
(20) Newkome, G. R.; Roper, J . M. J . Org. Chem. 1979, 44, 502.

6706 J . Org. Chem., Vol. 63, No. 19, 1998
Katritzky et al.
Ta ble 1. Su m m a r y of Ster eoselective Olefin a tion s
(Sch em e 1)
Ta ble 2. Su m m a r y of Ster eoselective Olefin a tion s To
F or m Dien es (Sch em e 2)
a
A (TiCl3/Li), B (TiCl3/Li, THF), C (TiCl3/Zn-Cu), D (TiCl3/Zn-
b
Cu, NEt3), E (TiCl4/Zn-Cu, NEt3). Overall yield based on 1.
c Determined by GCMS. Decomposed on standing, therefore not
d
fully characterized.
Ta ble 3. Su m m a r y of Ster eoselective Olefin a tion s To
F or m Tr ien es (Sch em e 3)
a
b
E (TiCl4/Zn-Cu, NEt3). Overall yield based on 5. c Deter-
mined by GCMS.
clearly indicates that using 1-allylbenzotriazoles to ap-
proach the diene system avoids these side reactions. It
is also noted that no 1,4-addition was detected in during
the preparation of 9b, and the yields of the reductive
elimination for 7h ,i were satisfactory.
a
A (TiCl3/Li), B (TiCl3/Li, THF), C (TiCl3/Zn-Cu), D (TiCl3/Zn-
b
Cu, NEt3), E (TiCl4/Zn-Cu, NEt3). Overall yield based on 1.
c Determined by GCMS. Temperature raised to 60 °C for the
d
preparation of 3k . e Temperature raised to 23 °C for the prepara-
tion of 3l. f Lithiation was followed by transmetallation with CeCl3
prior to addition of tetralone.
Tr a n sm eta la tion w ith Cer iu m . Initially lithiation
of substrate 1d followed by treatment with tetralone 2j
did not give the desired â-hydroxybenzotriazole derivative
3m due to proton transfer to the lithiated species.
Instead only the starting materials were recovered. The
transmetalation of organolithiums with cerium trichlo-
ride to form the less basic organoceriums has been shown
to result in smooth reactions with carbonyl compounds
even though the substrates are susceptible to enolization
or metal-halogen exchange with organolithiums.21 Trans-
metalation of lithiated 1d with cerium trichloride and
low-valent titanium conditions using 1-(2-pyridylmethyl)-
benzotriazole 1f. The yields of 2-pyridyl derivative 4l in
the absence and presence of triethylamine were 18% and
27%, respectively.
Con ju ga ted Ald eh yd es. For R,â-unsaturated carbo-
nyl compounds 8a -c, undesired 1,4-additions were en-
countered in the nucleophilic addition step. Intermo-
lecular reductive coupling of allylic alcohols8a is a possible
side reaction in the reductive elimination step. The
higher yield of 7c (Table 2 entry 3 compared to entry 8)

Trans-Selective Olefination of CO Compounds
J . Org. Chem., Vol. 63, No. 19, 1998 6707
tives is described for the preparation of di-, tri-, and
tetrasubstituted alkenes, dienes, and a triene. Although
an aryl, heteroaryl, or allyl group is present in benzo-
triazole derivatives 1 and 5, we do not believe this method
is limited to such starting materials. This method offers
good stereoselectivity without any need to isolate dias-
tereoisomeric intermediates together with easy isolation
of the products and constitutes a simple procedure which
complements the Wittig, Peterson, and J ulia reactions.
Exp er im en ta l Section
Melting points were determined on a hot stage apparatus
without correction. NMR spectra were obtained at 300 MHz
for 1H and 75 MHz for 13C NMR spectra in chloroform-d;
chemical shift values are reported as δ downfield from TMS
as an internal standard for 1H and solvent as the internal
standard for 13C. The NMR spectra reported were for the trans
isomers unless otherwise stated. Mass spectra and elemental
analyses were performed within the department.
THF and DME were distilled under nitrogen immediately
prior to use from a blue solution containing benzophenone/
sodium. The Zn-Cu couple was prepared according to the
literature procedure.23 Column chromatography was carried
out on MCB silica gel (230-400 mesh). Other chemicals were
used as obtained from commercial sources. Reactions were
routinely carried out under an argon atmosphere with mag-
netic stirring.
F igu r e 1.
treatment with tetralone 2j gave the intermediate 3m
in situ. Olefination under low-valent titanium conditions
gave olefin 4m in high yield.
Ter tia r y Su bstr a te 1d . The use of the tertiary
substrate 1d and ketones 2g,h ,j leads to tetrasubstituted
olefins 4g,h ,m in consistently high yields. The difficul-
ties in the formation of tri- and tetrasubstituted products
is a limitation of the J ulia reaction.22
NOE Exp er im en ts. NOE experiments were per-
formed to determine the configuration of the olefin bond
formed by the low-valent titanium methodology. The
following significant enhancements (5-10% when methyl
protons or 2-6% when olefinic protons were irradiated)
were observed (Figure 1). For compound 4d , NOE were
observed on the olefinic signal (6.28 ppm) when the tert-
butyl protons (1.34 ppm) were irradiated and on the
aromatic protons (7.12 ppm) when the methyl protons
(1.79 ppm) were irradiated. Irradiation of the methyl
protons (2.05 ppm) in 4e gave a NOE enhancement of
the methine proton (2.35 ppm). When the methyl protons
(2.28 and 2.37 ppm) of 4f were irradiated, no NOE
enhancement of the olefinic signal (6.81 ppm) was
detected. Whereas when the olefinic proton was irradi-
ated, NOE enhancement was observed on the phenyl
protons (7.25 ppm).
For compound 4o and 7d , NOE were observed on
protons a (6.64 and 5.96 ppm) when the aromatic and
methyl protons (7.65 and 1.10 ppm) were irradiated,
respectively. The assignment of protons a and the
aromatic protons were made on the basis of the coupling
constants and splitting patterns observed in the 1H NMR
spectra. NOE enhancement of the proton a and b signals
(6.33 and 5.59 ppm) of 7g were observed when the methyl
protons (1.75 ppm) and the methine proton (4.76 ppm)
were irradiated, respectively (Figure 1). The geometry
of the remaining examples was assigned by analogy.
P r ep a r a tion of 1-(Ben zotr ia zol-1-yl)-1-p h en yleth a n e
(1d ). A mixture of (1-bromoethyl)benzene (3.7 g, 20 mmol),
benzotriazole (2.86 g, 24 mmol), triethylamine (2.63 g, 26
mmol), and toluene (100 mL) was refluxed for 4 h. On cooling
the reaction mixture was washed with 10% Na2CO3 (2 × 100
mL) and water (100 mL) and dried (anhydrous MgSO4). The
solvent was removed in vacuo, and the residue was recrystal-
lized from hexane/ethyl acetate (1:1, 10 mL) to give the product
1
1d 24 (2.81 g, 63%): oil; H NMR δ 2.16 (d, J ) 7.2 Hz, 3 H),
6.05 (q, J ) 7.2 Hz, 1 H), 7.22-7.34 (m, 8 H), 8.04 (d, J ) 6.9
Hz, 1 H); 13C NMR δ 21.1, 59.0, 110.1, 119.9, 123.8, 126.3,
126.9, 128.2, 128.9, 132.4, 140.2, 146.4.
P r oced u r e for Gen er a t in g Low -Va len t Tit a n iu m .
Meth od A. Lithium wire (1.05 g, 75 mmol) and TiCl3 (6.94 g,
45.0 mmol) were added under argon to a 250 mL three-neck
flask, and the system was degassed and protected with argon.
Dry DME (100 mL) was added and the mixture refluxed 1 h.
Meth od B. The same as method A, but using dry THF (100
mL) as solvent. Meth od C. Zn-Cu couple (5.4 g) and TiCl3
(3.8 g, 15 mmol) were added under argon to a 250 mL three-
neck flask, and the system was degassed and protected with
argon. While stirring, dry DME (40 mL) was added via syringe
and the mixture was refluxed for 4 h. Meth od D. The same
as method C, but triethylamine was added. Meth od E. Dry
DME (40 mL) was added to a 250 mL three-neck flask
containing Zn-Cu couple (5.8 g) under argon. The system was
degassed, protected with argon, and cooled to -10 °C (ice-
NH4Cl bath). TiCl4 (2.5 mL, 22.9 mmol) was added dropwise
via syringe while the mixture was stirred. The bath was
removed and the mixture heated at reflux for 3 h. Triethyl-
amine (1.0 mL) was added via syringe and the reflux continued
for 1 h.
Gen er a l P r oced u r e for Olefin a tion . Compounds 1a -h
and 5a -d (4.8 mmol) were dissolved with THF (20 mL) in a
lithiation bottle under argon and cooled to -78 °C. n-BuLi
(3.2 mL, 1.6 M, 5.1 mmol) was added dropwise. The dark
colored solution was stirred for 10 min followed by addition of
the corresponding carbonyl compound 2a -n and 8a -c (5.3
mmol) in dry THF (3.0 mL). The temperature was raised if
necessary (see Table 1). After the dark color disappeared, the
mixture was immediately quenched with saturated NaHCO3
(20 mL). On warming, ether (30 mL) was added, and the
organic phase was separated and dried (anhydrous Na2SO4).
Concentration under reduced pressure gave a crude mixture
of â-hydroxybenzotriazole 3a -m , 6a -g, 9a -d , and 10a dia-
stereomers.
Con clu sion
A convenient and stereocontrolled olefination of alde-
hydes and ketones with a variety of benzotriazole deriva-
(21) Imamoto, T.; Kusumoto, T.; Tawarayama, Y.; Sugiura, Y.; Mita,
T.; Hatanaka, Y.; Yokoyama, M. J . Org. Chem. 1984, 49, 3904.
(22) (a) Kocienski, P. Phosphorus Sulfur 1985, 24, 97. (b) Kocienski,
P. J . Chem. Ind. (London) 1981, 548.
(23) McMurry, J . E.; Fleming, M. P.; Kees, K. L.; Krepski, L. R. J .
Org. Chem. 1978, 43, 3255.
(24) Katritzky, A. R.; Puschmann, I. B.; Stevens, C. V.; Wells, A. P.
J . Chem. Soc., Perkin Trans. 2 1995, 1645.
(25) Asokan, C. V.; Ila, H.; J unjappa, H. Synthesis 1987, 284.
(26) Campbell, A.; Kenyon, J . J . Chem. Soc. 1947, 436.

6708 J . Org. Chem., Vol. 63, No. 19, 1998
Katritzky et al.
The crude â-hydroxybenzotriazole 3a -m , 6a -g, 9a -d , and
10a diastereomers were dissolved in dry DME (2 × 15 mL)
under argon and transferred via syringe to the low-valent
titanium reaction media described above. The mixture was
refluxed (see Tables 1, 2, and 3 for time). On cooling, hexane
(50 mL) was added and the reaction mixture filtered and
washed with hexane (50 mL). The solid residue was dispersed
in water (50 mL) and extracted with hexane (50 mL). The
combined organics were washed with 10% Na2CO3 (2 × 50 mL)
and water (50 mL) and dried (anhydrous Na2SO4). Solvent
was removed in vacuo followed by silica gel column chroma-
tography with hexane as the eluent to give the product 4a -
m , 7a -j, and 11a . (For 4k and 4l ether was used instead of
hexane to extract the product and hexane/ethyl acetate (2:1)
was used as the eluent for column chromatography.)
133.6, 137.5. Anal. Calcd for C17H21N: C, 85.30; H, 8.85; N,
5.85. Found: C, 85.38; H, 9.02; N, 5.80.
1-Meth yl-3-[(E)-2-ph en yl-1-pr open yl]-1H-in dole (4j): mp
81-83 °C; 1H NMR δ 2.36 (s, 3 H), 3.80 (s, 3 H), 7.05 (s, 1 H),
7.12-7.40 (m, 7 H), 7.56 (d, J ) 7.5 Hz, 2 H), 7.74 (d, J ) 7.8
Hz, 1 H); 13C NMR δ 18.7, 32.9, 109.2, 113.3, 118.4, 119.1,
119.5, 122.1, 125.8, 126.4, 127.4, 128.3, 133.3, 136.4, 144.6.
Anal. Calcd for C18H17N: C, 87.41; H, 6.93; N, 5.66. Found:
C, 87.23; H, 7.20; N, 5.67.
2-[(E)-3,3-Dim eth ylbu ten yl]p yr id in e (4k ): oil; 1H NMR
δ 1.15 (s, 9 H), 6.41 (d, J ) 16.2 Hz, 1 H), 6.78 (d, J ) 15.9 Hz,
1 H), 7.08 (t, J ) 6.3 Hz, 1 H), 7.26 (d, J ) 7.8 Hz, 1 H), 7.59
(t, J ) 9.3 Hz, 1 H), 8.53 (d, J ) 4.2, 1 H); 13C NMR δ 29.4,
33.5, 121.1, 121.5, 125.0, 136.3, 146.2, 149.4, 156.5; HRMS
calcd for C11H13N 161.1204, found 161.1187.
1-Meth yl-4-[(E)-2-p h en yl-1-eth en yl]ben zen e (4a ): mp
2-[(E)-2-(4-Meth ylp h en yl)-1-eth en yl]p yr id in e (4l): mp
1
118-119 °C (lit.25 mp 119-120 °C); H NMR δ 2.36 (s, 3 H),
1
83-85 °C; H NMR δ 2.38 (s, 3 H), 7.10-7.21 (m, 4 H), 7.38
7.07 (s, 1 H), 7.08 (s, 1 H), 7.17 (d, J ) 8.0 Hz, 2 H), 7.22-7.27
(m, 1 H), 7.35 (t, J ) 7.7 Hz, 2 H), 7.42 (d, J ) 8.2 Hz, 2 H),
7.52 (d, J ) 7.2 Hz, 2 H); 13C NMR δ 21.3, 126.4, 126.4
(overlapped), 127.4, 127.7, 128.6, 129.4, 134.6, 137.5.
1-(Cycloh exylid en em eth yl)-4-m eth ylben zen e (4b): oil;
1H NMR δ 1.27-1.68 (m, 6 H), 2.25 (t, J ) 6.0 Hz, 2 H), 2.33
(s, 3 H), 2.37 (t, J ) 6.0 Hz, 2 H), 6.20 (s, 1 H), 7.07-7.23 (m,
4 H); 13C NMR δ 21.1, 26.7, 27.9, 28.5, 29.5, 37.7, 121.8, 128.7,
128.8, 135.3, 135.5, 142.8; HRMS calcd for C14H18 186.1409
(M+), found 186.1401.
1-Ch lor o-4-[(E)-1-p en ten yl]ben zen e (4c): oil; 1H NMR δ
0.96 (t, J ) 7.4 Hz, 3 H), 1.44-1.54 (m, 2 H), 2.15-2.22 (m, 2
H), 6.19 (dt, J ) 15.8, 7.6 Hz, 1 H), 6.33 (d, J ) 15.8 Hz, 1 H),
7.17-7.27 (m, 4 H); 13C NMR δ 13.7, 22.4, 35.1, 127.1, 128.6,
128.7, 131.7, 132.3, 136.4; HRMS calcd for C11H13Cl 180.0706
(M+), found 180.0704.
(d, J ) 7.5 Hz, 1 H), 7.50 (d, J ) 8.1 Hz, 2 H), 7.59-7.68 (m,
2 H), 8.61 (d, J ) 4.2 Hz, 1 H); 13C NMR δ 21.3, 121.8, 121.9,
127.0, 129.0, 129.4, 132.7, 133.9, 136.4, 138.3, 149.6, 155.8.
Anal. Calcd for C14H13N: C, 86.11; H, 6.72; N, 7.18. Found:
C, 85.86; H, 7.07; N, 6.96.
1-(P h en ylm eth ylm eth ylen yl)-1,2,3,4-tetr a h yd r on a p h -
th ylen e (4m ) (mixture of cis and trans isomers 1:1.7): oil;
1H NMR δ 1.73 (quintet, J ) 6.5 Hz, 2 H, cis), 1.86 (quintet,
J ) 6.5 Hz, 2 H, trans), 2.16 (s, 3 H, trans), 2.25 (s, 3 H, cis),
2.52-2.76 (m, 4 H, cis and trans), 6.55-7.50 (m, 9 H, cis and
trans); 13C NMR δ 22.0, 23.3, 23.5, 23.7, 28.8, 29.4, 29.5, 30.5,
124.5, 124.8, 125.7, 125.9, 126.2, 126.5, 127.2, 127.9, 128.1,
128.2, 128.4, 128.9, 129.2, 130.6, 131.9, 132.3, 132.4, 132.8,
137.0, 137.8, 139.8, 140.2, 145.3, 145.6. Anal. Calcd for
C
18H18: C, 92.25; H, 7.75. Found: C, 92.23; H, 7.85.
1-[(1E)-1,3-Bu ta d ien yl]n a p h th a len e (7a ): oil;29 1H NMR
1-(4-Ch lor op h en yl)-4-(E)-2,3,3-tr im eth yl-1-bu ten e (4d ):
oil; 1H NMR δ 1.34 (s, 9 H), 1.79 (s, 3 H), 6.28 (s, 1 H), 7.12 (d,
J ) 8.6 Hz, 2 H), 7.25 (d, J ) 8.6 Hz, 2 H); 13C NMR δ 14.4,
29.1, 36.7, 120.8, 128.0, 130.4, 131.4, 137.9, 147.8. Anal. Calcd
for C13H17Cl: C, 74.81; H, 8.21. Found: C, 74.96; H, 8.51.
1-[(E)-2-P h en yl-1-p r op en yl]cycloh exa n e (4e): oil; 1H
NMR δ 1.09-1.41 (m, 5 H), 1.60-1.78 (m, 5 H), 2.05 (s, 3 H),
2.32-2.40 (m, 1 H), 5.64 (d, J ) 8.7 Hz, 1 H), 7.17-7.41 (m, 5
H); 13C NMR δ 15.8, 26.0, 26.1, 33.0, 37.8,125.6, 126.4, 128.1,
132.8, 134.6, 144.1. Anal. Calcd for C15H20: C, 89.94; H, 10.06;
Found: C, 89.78; H, 10.45.
1-(4-Meth ylph en yl)-2-ph en yl-(E)-1-pr open e (4f): mp 48-
49 °C; 1H NMR δ 2.28 (s, 3 H), 2.37 (s, 3 H), 6.81 (s, 1 H), 7.18
(d, J ) 8.0 Hz, 2 H), 7.22-7.29 (m, 3 H), 7.36 (t, J ) 7.4 Hz,
2 H), 7.51 (d, J ) 7.5 Hz, 2 H); 13C NMR δ 17.5, 21.2, 126.0,
127.0, 127.6, 128.3, 128.9, 129.1, 135.5, 136.1, 136.7, 144.1.
Anal. Calcd for C16H16: C, 92.25; H, 7.75. Found: C, 92.02;
H, 7.91.
1,1,2-Tr ip h en yl-1-p r op en e (4g): mp 83-85 °C (lit.26 mp
93 °C); 1H NMR δ 2.14 (s, 3 H), 6.87-6.91 (m, 2 H), 6.95-7.05
(m, 3 H), 7.06-7.19 (m, 5 H), 7.20-7.28 (m, 3 H), 7.31-7.38
(m, 2 H); 13C NMR27 δ 23.3, 125.8, 126.2, 126.5, 127.4, 127.8,
128.1, 129.2, 129.9, 130.8, 135.7, 139.3, 143.0, 143.5, 144.0.
Anal. Calcd for C21H18: C, 93.29; H, 6.71; Found: C, 93.11;
H, 6.95.
δ 5.23 (d, J ) 9.9 Hz, 1 H), 5.38 (d, J ) 16.5 Hz, 1 H), 6.59-
6.72 (m, 1 H), 6.84 (dd, J ) 15.3 and 10.5 Hz, 1 H), 7.33 (d, J
) 15.0 Hz, 1 H), 7.38-7.53 (m, 3 H), 7.66 (d, J ) 7.2 Hz, 1 H),
7.76 (d, J ) 8.1 Hz, 1 H), 7.81-7.85 (m, 1 H), 8.13 (d, J ) 7.2
Hz, 1 H)); 13C NMR δ 117.9, 123.4, 123.6, 125.6, 125.7, 126.0,
128.0, 128.6, 129.6, 131.2, 132.4, 133.6, 133.7, 137.4. Anal.
Calcd for C14H12: C, 93.29; H, 6.71. Found: C, 93.28; H, 7.16.
1-[(E)-2-P r op en ylid en e]-1,2,3,4-t et r a h yd r on a p h t h a -
len e (7b): oil; 1H NMR δ 1.85 (quintet, J ) 6.3 Hz, 2 H), 2.66
(t, J ) 6.0 Hz, 2 H), 2.78 (t, J ) 6.0 Hz, 2 H), 5.18 (d, J ) 9.6
Hz, 1 H), 5.33 (d, J ) 16.5 Hz, 1 H), 6.64 (d, J ) 11.1 Hz, 1 H),
6.72-6.85 (m, 1 H), 7.07-7.19 (m, 3 H), 7.63-7.66 (m, 1 H);
13C NMR δ 23.0, 26.9, 30.5, 117.2, 123.6, 123.8, 126.1, 127.1,
128.9, 133.1, 135.7, 136.3, 138.1; HRMS calcd for C13H14
170.1096, found 170.1109.
(E,E)-1,4-Dip h en yl-1,3-bu ta d ien e (7c): mp 154-155 °C;
1H NMR δ 6.64-6.71 (m, 2 H), 6.90-6.95 (m, 2 H), 7.19-7.25
(m, 2 H), 7.32 (t, J ) 7.2 Hz, 4 H), 7.43 (d, J ) 7.2 Hz, 4 H);
13C NMR δ 125.4, 127.4, 128.6, 129.3, 131.8, 136.4. Anal. Calcd
for C16H14: C, 93.16; H, 6.84. Found: C, 92.96; H, 7.22.
1-Met h yl-2-[3-p h en yl-2-p r op en ylid en yl]cycloh exa n e
(7d ) (mixture of trans,cis and trans,trans isomers 1:4.3): oil;
1H NMR δ 1.10 (d, J ) 6.7 Hz, 3 H, trans,trans), 1.15 (d, J )
6.7 Hz, 3 H, trans,cis), 1.09-1.87 (m, 6 H), 1.98-2.11 (m, 1
H), 2.15-2.23 (m, 1 H, trans,trans), 2.29-2.44 (m, 1 H, trans,
cis), 2.75-2.81 (m, 1 H, trans,trans), 3.12-3.24 (m, 1 H, trans,
cis), 5.90 (d, J ) 11.4 Hz, 1 H, trans,cis), 5.96 (d, J ) 10.8 Hz,
1 H, trans,trans), 6.43 (d, J ) 15.8 Hz, 1 H, trans,cis), 6.49 (d,
J ) 15.6 Hz, 1 H, trans,trans), 7.02-7.12 (m, 1 H), 7.15 (t, J
) 6.1 Hz, 1 H), 7.27 (t, J ) 7.6 Hz, 2 H), 7.38 (d, J ) 7.5 Hz,
2 H); 13C NMR δ 18.6, 25.4, 28.2, 29.0, 36.8, 38.9, 119.7, 125.1,
126.0, 126.8, 128.5, 130.2, 138.2, 148.6; HRMS calcd for C16H20
212.1565 (M+), found 212.1565.
1-[1,2-Diph en ylpr open yl]-2,4-dim eth ylben zen e (4h ): mp
1
101-103 °C; H NMR δ 1.94 (s, 3 H), 2.20 (s, 3 H), 2.32 (s, 3
H), 6.86-7.17 (m, 13 H); 13C NMR δ 19.5, 21.1, 23.1, 125.6,
126.2, 126.5, 127.3, 127.9, 129.2, 129.7, 130.3, 131.0, 135.8,
135.9, 136.3, 138.1, 139.9, 141.9, 143.8. Anal. Calcd for
C
23H22: C, 92.57; H, 7.43. Found: C, 92.27; H, 7.74.
3-[(E)-2-Cycloh exyl-1-eth en yl]-1-m eth yl-1H-in d ole (4i):
oil; 1H NMR δ 1.10-1.40 (m, 5 H), 1.60-1.95 (m, 5 H), 2.08-
2.20 (m, 1 H), 3.73 (s, 3 H), 6.12 (dd, J ) 16.2 and 6.9 Hz, 1
H), 6.50 (d, J ) 16.2 Hz, 1 H), 7.03 (s, 1 H), 7.10-7.29 (m, 3
H), 7.83 (d, J ) 8.1 Hz, 1 H); 13C NMR δ 26.2, 26.3, 32.7, 33.5,
41.7, 109.3, 114.2, 119.4, 119.5, 120.1, 121.8, 126.3, 126.8,
(1E,3E)-5-Meth yl-1-p h en yl-1,3-h exa d ien e (7e): oil; 1H
NMR δ 1.06 (d, J ) 6.7 Hz, 6 H), 2.35-2.46 (m, 1 H), 5.81 (dd,
J ) 15.3 Hz, 6.8 Hz, 1 H), 6.18 (dd, J ) 15.3 Hz, 10.3 Hz, 1
H), 6.46 (d, J ) 15.7 Hz, 1 H), 6.75 (dd, J ) 15.7 Hz, 10.5 Hz,
(27) The 13C NMR data previously published28 were inconsistent
with our results. When notified the authors repeated their analysis
and found the same values as reported here.
(28) Santiago, A. N.; Lassaga, G.; Rappoport, Z.; Rossi, R. A. J . Org.
Chem. 1996, 61, 1125.
(29) Bailey, A. S.; Shuttleworth, A. J . J . Chem. Soc. C 1968, 1115.

Trans-Selective Olefination of CO Compounds
J . Org. Chem., Vol. 63, No. 19, 1998 6709
1 H), 7.18 (t, J ) 7.1 Hz, 1 H), 7.29 (t, J ) 7.5 Hz, 2 H), 7.37
(d, J ) 7.4 Hz, 2 H); 13C NMR δ 22.3, 31.3, 126.1, 127.0, 127.6,
128.5, 129.6, 130.2, 137.3, 142.8; HRMS calcd for C13H16
172.1252 (M+), found 172.1252.
1,1-Dip h en yl-4-m eth yl-1,3-p en ta d ien e (7f): oil; 1H NMR
δ 1.76 (s, 3 H), 1.89 (s, 3 H), 5.94 (d, J ) 11.3 Hz, 1 H), 6.89
(d, J ) 11.3 Hz, 1 H), 7.18-7.40 (m, 10 H); 13C NMR δ 18.6,
26.4, 123.2, 124.5, 126.9, 127.0, 127.4, 128.0, 128.1, 130.6,
137.5, 139.8, 140.2, 143.1. Anal. Calcd for C18H18: C, 92.26;
H, 7.74. Found: C, 92.16; H, 8.06.
1,1-Dip h en yl-2-m eth yl-2,4-h exa d ien e (7g): oil; 1H NMR
δ 1.76 (d, J ) 7.3 Hz, 3 H), 1.77 (s, 3 H), 4.76 (s, 1 H), 5.48-
5.61 (m, 1 H), 5.59 (d, J ) 10.0 Hz, 1 H), 6.28-6.38 (m, 1 H),
7.12-7.31 (m, 10 H); 13C NMR δ 17.5, 18.3, 60.1, 126.2, 127.8,
128.2, 128.3, 128.7, 129.4, 137.5, 142.5; HRMS calcd for C19H20
248.1565 (M+), found 248.1542.
1,4-Dip h en yl-1,3-p en t a d ien e (7h ) (mixture of trans,cis
and trans,trans isomers 1:2): mp 66-69 °C; 1H NMR δ (trans-
trans) 2.29 (s, 3 H), 6.52-6.71 (m, 2 H), 7.10-7.52 (m, 11 H);
(trans-cis) 2.20 (s, 3 H), 6.32 (d, J ) 10.8 Hz, 1 H), 6.55 (d, J
) 15.6 Hz, 1 H), 6.88 (dd, J ) 15.6 Hz, 10.8 Hz, 1 H), 7.10-
7.52 (m, 10 H); 13C NMR δ (mixture of trans-trans and trans-
cis) 16.2, 25.6, 125.6, 125.8, 126.3, 126.4, 126.66, 126.71,
127.09, 127.14, 127.3, 127.4, 127.6, 128.2, 128.3, 128.4, 128.5,
128.6, 131.4, 132.9, 136.8, 137.8, 139.6, 143.0. Anal. Calcd
for C17H16: C, 92.67; H, 7.33. Found: C, 92.37; H, 7.79.
1-(N,N-Dieth yla m in o)p h en yl-4-m eth yl-(E,E)-1,3-p en ta -
1
d ien e (7i): oil; H NMR δ 1.15 (t, J ) 7.2 Hz, 6 H), 1.82 (s, 3
H), 1.83 (s, 3 H), 3.35 (q, J ) 7.2 Hz, 4 H), 5.96 (d, J ) 11.1
Hz, 1 H), 6.34 (d, J ) 15.6 Hz, 1 H), 6.62 (d, J ) 8.7 Hz, 2 H),
6.77 (dd, J ) 15.6, 11.1 Hz, 1 H), 7.26 (d, J ) 8.7 Hz, 2 H); 13
C
NMR δ 12.6, 18.4, 26.1, 44.4, 111.8, 121.3, 125.7, 126.0, 127.3,
129.9, 133.2, 146.9. Anal. Calcd for C16H23N: C, 83.79; H,
10.11; N, 6.11. Found: C, 83.55; H, 10.56; N, 6.23.
2-Met h yl-5-[(3-m et h yl-2-cycloh exen ylid en e)m et h yl]-
th iop h en e (7j): 1H NMR δ 1.72-1.76 (m, 2 H), 1.80 (s, 3 H),
2.07 (t, J ) 5.9 Hz, 2 H), 2.46 (s, 3 H), 2.58 (t, J ) 6.1 Hz, 2
H), 5.93 (s, 1 H), 6.24 (s, 1 H), 6.64 (d, J ) 2.5 Hz, 1 H), 6.73
(d, J ) 3.1 Hz, 1 H); 13C NMR δ 15.3, 22.6, 24.1, 26.3, 30.2,
117.7, 125.1, 126.4, 126.9, 135.2, 138.5, 138.9, 139.7.
(1E,3E)-6-Meth yl-1-p h en yl-1,3,5-h ep ta tr ien e (11a ): oil;
1H NMR δ 1.81 (s, 3 H), 1.82 (s, 3 H), 5.93 (d, J ) 11.1 Hz, 1
H), 6.27 (dd, J ) 10.8, 10.5 Hz, 1 H), 6.40-6.60 (m, 2 H), 6.86
(dd, J ) 15.6, 10.5 Hz, 1 H), 7.16-7.45 (m, 5 H)); 13C NMR δ
18.5, 26.2, 125.5, 126.1, 126.3, 127.1, 127.5, 128.5, 129.7, 130.2,
130.3, 130.8; HRMS calcd for C14H16 184.1252 (M+), found
184.1289.
J O980616V