Molybdenum(II)-catalyzed allylation of electron-rich aromatics and heteroaromatics

Article abstract of DOI:10.1021/jo982178y

The stable, readily available molybdenum(II) complexes [Mo(CO)₄Br₂]₂ (B) and Mo(CO)₃(MeCN)₂-(SnCl₃)Cl (C) have been found to catalyze C-C bond- forming allylic substitution with electronrich aromatics (e.g., 15 + PhOMe → 62) and heteroaromatics (e.g., 15 + 36 → 88) as nucleophiles under mild conditions (room temperature, 30 min-3 h). Remarkable is the para-selectivity for anisole, whereas phenol tends to favor ortho-substitution in certain instances. Mechanistic and stereochemical experiments are indicative of Lewis-acid catalysis rather than a metal template-controlled process.

Full text of DOI:10.1021/jo982178y

J . Org. Chem. 1999, 64, 2751-2764
2751
Molybd en u m (II)-Ca ta lyzed Allyla tion of Electr on -Rich Ar om a tics
a n d Heter oa r om a tics
Andrei V. Malkov,† Stuart L. Davis,† Ian R. Baxendale,†,‡ William L. Mitchell,§ and
Pavel Kocˇovsky´*,†
Department of Chemistry, University of Leicester, Leicester LE1 7RH, U.K., and
Receptor Chemistry Unit, GlaxoWellcome PLC, Stevenage, Herts SG1 2NY, U.K.
Received October 29, 1998
The stable, readily available molybdenum(II) complexes [Mo(CO)4Br2]2 (B) and Mo(CO)3(MeCN)2-
(SnCl3)Cl (C) have been found to catalyze C-C bond-forming allylic substitution with electron-
rich aromatics (e.g., 15 + PhOMe f 62) and heteroaromatics (e.g., 15 + 36 f 88) as nucleophiles
under mild conditions (room temperature, 30 min-3 h). Remarkable is the para-selectivity for
anisole, whereas phenol tends to favor ortho-substitution in certain instances. Mechanistic and
stereochemical experiments are indicative of Lewis-acid catalysis rather than a metal template-
controlled process.
Sch em e 1
In tr od u ction
Allylic substitution catalyzed by palladium(0) and
other transition metal complexes (Mo, W, Fe, Co, Ni) is
a well-established methodology in organic synthesis.1
This now classical reaction is generally stereospecific and,
in the case of Pd(0) and malonate-type nucleophiles,
normally occurs via a double inversion of configuration
(inv-inv), involving η3-complexes 2 (M ) Pd)2 as inter-
mediates (Scheme 1). With organometallics and a Pd(0)3
or Ni(0)4 catalyst, an inv-ret pathway is observed, result-
ing in an overall inversion. The complementary ret-inv
mechanism has been reported for substrates capable of
precoordination of Pd(0)5-7 and for stoichiometric, Mo-
(0)-mediated reactions involving isolation of the η3-
complexes 2.8 Finally, the ret-ret alternative has been
demonstrated for the Mo(0)-catalyzed reaction9,10 (in
contrast to the stoichiometric procedure). On the other
hand, allylic substitution catalyzed by strong Lewis acids
proceeds via uncoordinated allylic cations, which results
in stereochemical scrambling.
The Pd(0)-catalyzed allylic substitution has mainly
been developed to construct C-C bonds,1-3,5-7 although
formation of C-H, C-O, and C-N bonds has also been
reported.1,2g-i,5b Recently, Sinou11 has shown that phenols
and naphthols can be used as O-nucleophiles to obtain
arylallyl ethers, such as 5, provided carbonates (4), rather
than acetates, are employed as allylic substrates (Scheme
2). At higher temperature, the primarily formed â-naph-
thoxy derivative 5 undergoes a rearrangement to afford
the thermodynamic product 6,11 so that the reaction can,
a priori, be employed either as a C-O or C-C bond-
forming process.
* Correspondence author. E-mail: PK10@Le.ac.uk.
† University of Leicester.
‡ Current address: Department of Chemistry, University of Cam-
bridge, Cambridge CB2 1EW, U.K.
§ GlaxoWellcome PLC.
(1) Hegedus, L. S. Transition Metals in the Synthesis of Complex
Organic Molecules; University Science Books: Mill Valley, CA, 1994.
(2) For key references, see: (a) Trost, B. M.; Strege, P. E. J . Am.
Chem. Soc. 1975, 97, 2534. (b) Trost, B. M.; Verhoeven, T. R. J . Org.
Chem. 1976, 41, 3215. (c) Hayashi, T.; Hagihara, T.; Konishi, M.;
Kumada, M. J . Am. Chem. Soc. 1983, 105, 7767. For reviews, see: (d)
Trost, B. M. Tetrahedron 1977, 33, 371. (e) Trost, B. M. Acc. Chem.
Res. 1980, 13, 385. (f) Tsuji, J . Tetrahedron 1986, 42, 4361. (g) Frost,
C. G.; Howarth, J .; Williams, J . M. J . Tetrahedron: Asymmetry 1992,
3, 1089. (h) Trost, B. M. Pure Appl. Chem. 1996, 68, 779. (i) Trost, B.
M.; Van Vranken, D. L. Chem. Rev. 1996, 96, 395.
(3) Temple, J . S.; Schwartz, J . J . Am. Chem. Soc. 1980, 102, 7381.
(b) Matsushida, H.; Negishi, E. J . Chem. Soc., Chem. Commun. 1982,
160. (c) Temple, J . S.; Riediker, M.; Schwartz, J . J . Am. Chem. Soc.
1982, 104, 1310. (d) Labadie, J . W.; Stille, J . K. J . Am. Chem. Soc.
1983, 105, 6129. (e) Goliaszewski, A.; Schwartz, J . J . Am. Chem. Soc.
1984, 106, 5028. (f) Keinan, E.; Roth, Z. J . Org. Chem. 1983, 48, 1769.
(4) Consiglio, G.; Morandini, F.; Piccolo, O. J . Am. Chem. Soc. 1981,
103, 1846. (b) Consiglio, G.; Piccolo, O.; Roncetti, L.; Morandini, F.
Tetrahedron 1986, 41, 2043. (c) Didiuk, M. T.; Morken, J . P.; Hoveyda,
A. H. J . Am. Chem. Soc. 1995, 117, 7273. (d) Didiuk, M. T.; Morken,
J . P.; Hoveyda, A. H. Tetrahedron 1998, 54, 1117.
(5) Stary´, I.; Kocˇovsky´, P. J . Am. Chem. Soc. 1989, 111, 4981. (b)
Stary´, I.; Zaj´ıcˇek, J .; Kocˇovsky´, P. Tetrahedron 1992, 48, 7229. (c)
Kurosawa, H.; Ogoshi, S.; Kawasaki, Y.; Murai, S.; Miyoshi, M.; Ikeda,
I. J . Am. Chem. Soc. 1990, 112, 2813. (d) Kurosawa, H.; Kajimaru, H.;
Ogoshi, S.; Yoneda, H.; Miki, K.; Kasai, N.; Murai, S.; Ikeda, I. J . Am.
Chem. Soc. 1992, 114, 8417.
(6) Krafft, M. E.; Wilson, A. M.; Fu, Z.; Procter, M. J .; Dasse, O. A.
J . Org. Chem. 1998, 63, 1748.
(7) Farthing, C. N.; Kocˇovsky´, P. J . Am. Chem. Soc. 1998, 120, 6661.
In the adjacent paper,12 we have detailed the prepara-
tion of molybdenum(II) complexes A-C (Scheme 3) and
their tungsten(II) congeners and demonstrated their uti-
lization as Lewis-acidic catalysts in allylic substitution.13-16
Complexes A-C proved to catalyze both C-O and C-C
bond formation. Thus, allylic acetate 7 reacted with
(8) Faller, J . W.; Linebarrier, D. Organometallics 1988, 7, 1670. (b)
Ward, Y. D.; Villanueva, L. A.; Allred, G. D.; Liebeskind, L. S. J . Am.
Chem. Soc. 1996, 118, 897.
(9) Dvorˇa´k, D.; Stary´, I.; Kocˇovsky´, P. J . Am. Chem. Soc. 1995, 117,
6130.
(10) For demonstrating the overall retention of configuration in Mo-
(0)-catalyzed reactions, see: (a) Trost, B. M.; Lautens, M. J . Am. Chem.
Soc. 1982, 104, 5543. (b) Trost, B. M.; Lautens, M. J . Am. Chem. Soc.
1983, 105, 3343. (c) Trost, B. M.; Lautens, M. Organometallics 1983,
2, 1687. (d) Trost, B. M.; Lautens, M.; Peterson, B. Tetrahedron Lett.
1983, 24, 4525. (e) Trost, B. M.; Lautens, M. J . Am. Chem. Soc. 1987,
109, 1469. (f) Trost, B. M.; Lautens, M. Tetrahedron 1987, 43, 4817.
(g) Trost, B. M.; Merlic, C. A. J . Am. Chem. Soc. 1990, 112, 9590.
(11) Goux, C.; Massacret, M.; Lhoste, P.; Sinou, D. Organometallics
1995, 14, 4585.
(12) Malkov, A. V.; Baxendale, I. R.; Dvorˇa´k, D.; Mansfield, D. J .;
Kocˇovsky´, P. J . Org. Chem. 1999, 64, 2737-2750.
10.1021/jo982178y CCC: $18.00 © 1999 American Chemical Society
Published on Web 03/20/1999

2752 J . Org. Chem., Vol. 64, No. 8, 1999
Malkov et al.
Sch em e 2
Ch a r t 1
Ch a r t 2
Sch em e 3
Sch em e 4
allylic substitution in the presence of Mo(II) catalysts
A-C.12 It is, therefore, tempting to raise the question of
whether aromatics, such as anisole (14; R ) Me), can be
regarded as alkyl vinyl ethers and would react with an
allylic substrate. Furthermore, would phenol (14; R ) H)
serve as a nucleophilic enol? If successful, what would
be the regioselectivity regarding both the allylic substrate
and the aromatic ring, and what chemoselectivity can be
expected for phenol in view of the Sinou work (Scheme
2):11 O- or C-allylation? Finally, if C-C bond formation
is attained, would this be an example of direct, Friedel-
Crafts-type aromatic substitution or a two-step process
as that in the Scheme 2? Note that in classical Friedel-
Crafts reactions17,18 and related processes, the Lewis-
acidic catalyst has to be used, as a rule, in stoichiometric
amounts owing to its trapping by coordination to the
product, which makes it unavailable for another catalytic
cycle. Hence, effective dissociation of the catalyst from
the product is crucial, and attempts at developing a new
system should focus on this step.
MeOH12,13 in the presence of either of the complexes A-C
(2-5 mol %) at room temperature to give the correspond-
ing methoxy-derivative 9 (Scheme 4). By contrast, cin-
namyl acetate 8 proved inert, suggesting that only those
allylic substrates that are capable of a fair degree of
stabilization of the allylic cation can be successfully
employed. The C-C bond formation with silyl enol ethers
as nucleophiles (e.g., 10) occurred under very mild
conditions even more readily (Scheme 4).12,13 Although
this particular reaction was not regioselective, producing
a ∼1:1 mixture of 11 and 12, we have described a number
of highly regioselective examples.12
To address these issues, we have employed a series of
allylic substrates (Chart 2) and a set of representative,
electron-rich aromatic and heteroaromatic compounds
Resu lts a n d Discu ssion
The electron-rich double bond in enol ethers, such as
13 (Chart 1), proved sufficiently nucleophilic to effect
(17) For overviews on the Friedel-Crafts reaction, see: (a) Roberts,
R. M.; Khalaf, A. A. Friedel-Crafts Alkylation Chemistry: A Century
of Discovery; M. Dekker: New York, 1984. (b) Heaney, H. In Compre-
hensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon:
Oxford, U.K., 1991; Vol. 2, pp 733 and 753. (c) Olah, G. A.; Krishna-
murti, R.; Prakash, G. K. S. Ibid, Vol. 3, p 893.
(18) Aside from the standard Friedel-Crafts reactions, allylation
of highly oxygenated aromatic rings with cationic organometallic
π-complexes has also been reported: (a) Harman, W. D.; Sekine, M.;
Taube, H. J . Am. Chem. Soc. 1988, 110, 5725. (b) Kopach, M. E.;
Gonzalez, J .; Harman, W. D. J . Am. Chem. Soc. 1991, 113, 8972. (c)
Kopach, M. E.; Harman, W. D. J . Org. Chem. 1994, 59, 6506. (d)
Malkov, A. V.; Mojovic, L.; Stephenson, G. R.; Turner, A. T.; Downie,
J . A.; Wilson, K. E.; Creaser C. S. Manuscript in preparation. For the
reactivity of Os-coordinated aromatics, see: (e) Kolis, S. P.; Kopach,
M. E.; Liu, R.; Harman, W. D. J . Org. Chem. 1997, 62, 130 and
references given therein.
(13) Dvorˇa´kova´, H.; Dvorˇa´k, D.; Sˇrogl, J .; Kocˇovsky´, P. Tetrahedron
Lett. 1995, 35, 6351. (b) Malkov, A. V.; Baxendale, I. R.; Mansfield, D.
J .; Kocˇovsky´, P. Tetrahedron Lett. 1997, 38, 4895. (c) Malkov, A. V.;
Davis, S. L.; Mitchell, W. L.; Kocˇovsky´, P. Tetrahedron Lett. 1997, 38,
4899.
(14) Abbott, A. P.; Malkov, A. V.; Zimmermann, N.; Raynor, J . B.;
Ahmed, G.; Steele, J . Kocˇovsky´, P. Organometallics 1997, 16, 3690.
(15) Bowden, J . A.; Colton, R. Aust. J . Chem. 1968, 21, 2657. (b)
Cotton, F. A.; Falvello, L. R.; Meadows, J . H. Inorg. Chem. 1985, 24,
514. (c) Cotton, F. A.; Poli, R. Inorg. Chem. 1987, 26, 1514.
(16) Baker, P. K.; Bury, A. J . Organomet. Chem. 1989, 359, 189. (b)
Baker, P. K.; Quinlan, A. J . Inorg. Chem. 1989, 28, 179. (c) Miguel,
D.; Perez-Martinez, J . A.; Garcia-Granda, S. Polyhedron 1991, 10, 1717.
(d) Cano, M.; Panizo, M.; Campo, J . A.; Tornero, J .; Menendez, N. J .
Organomet. Chem. 1993, 463, 121.

Molybdenum(II)-Catalyzed Allylation
J . Org. Chem., Vol. 64, No. 8, 1999 2753
Ta ble 1. Allyla tion of Ar om a tics w ith 7 a n d 8 Ca ta lyzed
by Com p lex Ba
Ch a r t 3
allylic aromatic
entry compd compd
product yield
time
Ph-OMe 1 h
product(s)
ratiob
(%)c
1
2
3
4
5
6
7
8
7
7
7
7
7
7
7
7
37
91
94
61
56
61
90
52
86
90
68
71
30f
78
70
57
44
Ph-OH
28
29
30
33
30 min
4 h
1 h
30 min
30 min
2 h
38 + 41
88:12
d
43d
44
45 + 48
54 + 56
58 + 60
59 + 61
(()-37
39
40 + 42
46
47 + 49
50 + 51
52 + 53
55 + 57
34:66
84:16
80:20
85:15
35
36
4 h
9
(R)-7 Ph-OMe 1 h
10
11
12
13
14
15
16
8
8
8
8
8
8
8
Ph-OMe 4 h
Ph-OH
28
30
31
1 h
6 he
3 h
6 h
6 h
5 h
83:17
81:19
79:21
77:23
75:25
32
33
Sch em e 5
a
The reactions were carried out on 0.5 mmol scale in CH2Cl2
with 5 mol % of the catalyst at room temperature under inert
b
atmosphere unless stated otherwise. The product ratios were
determined by 1H NMR spectra of the crude mixtures. c Isolated
d
yield. Contained ∼2% of a bis-allylated byproduct. e 2 mol % of
the catalyst. f Traces of a mixture of bis-allylated products were
also detected.
Sch em e 6
(Chart 3). Since the initial experiments with complex A
turned out to give poor conversions,13c we have focused
on complexes B and C.
Gen er a l Rea ctivity. At the outset, we have utilized
the readily available allylic acetate 7, which previously
proved fairly reactive toward a range of silyl enol ethers;12
anisole 26 and phenol 27 were selected as nucleophilic
probes (Scheme 5).
In the presence of dibromo complex B (5 mol %), 7
turned out to react with anisole at room temperature,
affording 37 as the sole product in 91% isolated yield
(Table 1, entry 1).19 Note that 37 was formed with high
selectivity by connecting the p-position of the aromatic
ring to the methyl terminus of the allylic system.20 Phenol
proved slightly less selective, giving a ∼7:1 mixture of
p- and o-products 38 and 41 (Table 1, entry 2). Allylation
with cinnamyl acetate 8 followed the same pattern:
anisole furnished solely the p-isomer 39 (Table 1, entry
10), whereas phenol gave a ∼5:1 mixture of p- and
o-products 40 and 42 (Table 1, entry 11). In both cases,
only attack at the less substituted terminus of the allylic
moiety was observed and the trans-configuration of the
double bond was preserved.
and 44, respectively (Table 1, entries 3 and 4).20 In the
case of the doubly activated nucleophile 30, preferential
formation of the isomer 45 (corresponding to o-substitu-
tion with respect to the hydroxy group) was observed.
However, in this instance, bis-allylated derivative 48 was
isolated as the major product (Table 1, entry 5),21 reflect-
ing the enhanced reactivity of the aromatic ring. Forma-
tion of the latter derivative could be partially (but not
entirely) suppressed by using an excess of 30 (typically
5 equiv). Cinnamyl acetate 8 exhibited similar reactivity
toward both 28 and 30, affording 46 and 47, respectively,
contaminated with the bis-allylated byproduct 49 in the
latter case (Table 1, entries 12 and 13).20
The unusually high p-selectivity, observed both with
anisole and phenol, raised the question of what would
be the result of blocking the p-position. To address this
issue, we have employed p-substituted aromatics 28-30
(Scheme 6). With 7, both p-methylanisole 28 and p-cresol
29 turned out to produce the corresponding o-isomers 43
The bis-allylation complicates the reaction of a highly
activated aromatic ring (i.e., one with two oxygen groups
attached) if a highly reactive allylic partner is utilized
(21) The bis(allyl) derivative was obtained as a ∼1:1 mixture of
diastereoisomers, which could not be separated and fully characterized.
However, the HRMS and NMR data are fully supportive of its
structure. Moreover, the latter problem was avoided by utilizing
cinnamyl acetate (8).
(19) This particular reaction is also completed at -10 °C in 30 min.
(20) The products structure was corroborated by NMR spectrometry,
including 2D-NMR experiments (e.g., NOESY) in more complicated
cases. For details, see the Experimental Section.

2754 J . Org. Chem., Vol. 64, No. 8, 1999
Malkov et al.
Sch em e 7
Sch em e 8
(Table 1, entry 5). Thus, 1,2-(methylenedioxy)benzene
(31) was found to mainly afford an inseparable diaste-
reoisomeric mixture of bis-allylated products on reaction
with 7. By contrast, employing the less reactive cinnamyl
acetate 8 (Scheme 7) resulted in a substantial reduction
of the rate of the second allylation so that 50 could be
isolated as the major product, whereas 51 was formed
only in a minute amount (Table 1, entry 14). Note that,
in this formation of 50 and 51, each allyl group was
introduced into the p-position with respect to one of the
oxygen atoms of the aromatic ring in 31.20 Similarly, a
∼3:1 mixture of mono- and bis-allylated products 52 and
53 was obtained on reaction of 8 with 3-methylveratrole
(32) (Table 1, entry 15); again, in 53, allyl groups are
located para to each of the MeO groups.20
Sch em e 9
As shown above, electron-rich aromatics proved to be
excellent reaction partners. By contrast, aromatics with
an adjacent electron-withdrawing group, such as Ph-
Cl, Ph-COMe, Ph-NO2, and m-chlorophenol were inert,
which is consistent with the assumed nucleophilic role
of the aromatic ring in these reactions. A methyl group
alone on the ring is apparently too weak to promote the
reaction, for toluene also proved inert (at room temper-
ature). Surprisingly, no reaction was observed with Ph-
OAc, Ph-NHCOMe, and Ph-NMe2 although these sub-
stituents are normally regarded as activating the aromatic
ring. This lack of reactivity can be attributed to inactiva-
tion of the catalyst by preferential coordination of the
metal to the Lewis-basic functional group (carbonyl or
nitrogen, respectively). The latter coordination is evi-
denced by IR spectroscopy: thus, for instance, adding an
equimolar amount of B to a solution of 8 in CH2Cl2 caused
a shift of ν(CdO) by 25 cm-1 (from 1740 to 1715 cm-1).
Similarly, a shift by 10 cm-1 was observed for benzalde-
hyde (from 1700 to 1690 cm-1). Furthermore, in both
instances, the relative intensities in the ν(CtO) region
of the complex have also changed: of the three maxima
at 1960 (vs), 2040 (s), and 2100 (w) cm-1, the latter was
moderately increased, indicating a change in the sym-
metry of the coordination sphere of the metal. With
acetamide as a model for amidic group, formation of a
precipitate was observed within 5 min after adding
complex B, demonstrating a strong coordination. This
behavior clearly shows that while coordination to the
acetate leaving group is essential for the allylic substitu-
tion to occur, the presence of another competing Lewis-
basic group in the molecule of one of the reaction partners
can engage the catalyst and prevent the reaction.
employed as representative model compounds (Scheme
8). 2-Methylfuran (33) was found to readily react with 7,
producing mainly 54 as the result of connecting the most
reactive 5-position20 of the furan ring with the methyl
terminus of the allyl moiety (Table 1, entry 6); 8 gave a
mixture of 55 and 57 (Table 1, entry 16). In the case of
indole 35 and its N-methyl derivative 36, the electrophilic
attack occurred exclusively at the expected 3-position20
(Table 1, entries 7and 8). Again, the reaction exhibited
high preference for the methyl terminus of the allylic
moiety, affording 58 and 59, respectively, in preference
to their regioisomers 60 and 61.22 By contrast, benzothi-
azole proved inert (presumably owing to deactivation of
the catalyst by coordination), whereas pyrrole produced
an intractable mixture. Carbazole, whose “indole â-posi-
tion” is blocked by the annulated ring, was also inert.
To establish the scope of this novel catalysis in
aromatic electrophilic substitution, we have examined the
reactivity of additional allylic acetates, namely 15-22
(Chart 2), toward our set of electron-rich aromatics
(Chart 3).
The reaction of 15 with anisole, carried out in the
presence of complex B, produced the expected p-isomer
62 (Scheme 9) at room temperature in 30 min (Table 2,
entries 1 and 2). The less reactive cyclohexenyl acetate
In view of the high reactivity of the electron-rich
aromatics, it was desirable to explore the potential
application of this method in heteroaromatic chemistry.
To this end, furan and indole derivatives 33-36 were
(22) In contrast to the ready reaction of both 35 and 36 with 7,
practically no reaction with 8 was detected.

Molybdenum(II)-Catalyzed Allylation
J . Org. Chem., Vol. 64, No. 8, 1999 2755
Ta ble 2. Ca ta lytic Allyla tion of Ar om a tics w ith 15-25a
entry
allylic compd
aromatic compd
catalyst
time
product(s)
62
product ratiob
yield (%)c
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
15
15
15
15
15
15
15
16
16
16
17
17
17
17
17
19
19
19
19
20
20
21
21
22
22
23
23
24
24
25
Ph-OMe
Ph-OMe
Ph-OH
Ph-OH
29
34
36
Ph-OH
29
B
B
B
C
B
B
B
B
B
B
B
C
B
C
C
B
B
B
B
B
B
B
B
B
B
B
C
B
B
B
30 min
3 hd
42
50
59
44
77
65
85
22e
80
70
56
73
79
83
91
50
41e
47
74
24e
19e
42
27e
47
48
59
50
75
51
72
62
20 min
20 min
30 min
30 min
30 min
30 min
30 min
30 min
2 h
1.5 h
30 min
30 min
2 h
2 h
20 min
2 h
2 h
2 h
2 h
1 h
1 h
1.5 h
2 h
63 + 73
63 + 66 + 73
74
87
88
64 + 75
76
89
36:64
11:43:46
36:64
36
Ph-OMe
Ph-OMe
Ph-OH
Ph-OH
29
Ph-OMe
Ph-OH
31
65 + 70
65 + 70
71f
57:43
54:46
90:10g
95:5g
71f
72f
84:16g
80:20g
87:13g
77f
78f
79
32
80
Ph-OMe
Ph-OH
Ph-OMe
Ph-OH
Ph-OMe
Ph-OH
Ph-OH
Ph-OH
Ph-OMe
Ph-OH
Ph-OMe
81f
85f,h
82i
95:5g
73:27j
90:10
>95:5j
80:20
90:10
90:10
86f
82i
86f
4 h
4 h
1 h
30 min
6 h
90 + 91k
90 + 91l
93m
92m
93
a
The reactions were carried out on 0.5 mmol scale in CH2Cl2 with 5 mol % of the catalyst at room temperature under inert atmosphere
unless stated otherwise. The product ratios were determined by 1H NMR spectra of the crude mixtures. c Isolated yield. At -10 °C.
b
d
e The low yield is mainly due to the competing elimination. fContained bis-allylated byproduct(s). The mono-/bis-allylation ratio. The
g
h
intermediate acyclic product was detected by TLC but not isolated; the reaction was quenched after the cyclization had been completed.
i
j
k
Contained ortho-isomer as byproduct. The para/ortho ratio. Contained the corresponding cis-isomers as byproducts, which were not
l
m
fully characterized; the trans/cis ratio was 81:19 for 90 and 75:25 for 91. The trans/cis ratio for 90 was 75:25. A 10-fold excess of the
aromatic nucleophile was used in order to suppress the bis-allylation.
Sch em e 10
17 afforded a ∼3:2 mixture of p- and o-isomers 65 and
70 (Table 2, entry 11); bimetallic catalyst C showed the
same behavior (Table 2, entry 12).
In contrast to anisole, phenol exhibited enhanced
proportion of the o-product on reaction with 15, giving
rise to a mixture of the p- and o-allylated phenols 63 and
66 and the bridged heterocycle 73 (Table 2, entries 3 and
4); the latter cyclic ether apparently originates from a
ring closure reaction of the intermediate o-substituted
phenol 66. With the p-position blocked, as in p-cresol 29,
the initially generated o-substituted product 67 (not
isolated) was cyclized to 74 in good yield (Table 2, entry
5). Isophoryl acetate 16 reacted in an analogous way with
both phenol 27 and p-cresol 29, affording a mixture of
p-allylated phenol 64 and the ring-closed heterocycle 75,
in the former case (Table 2, entry 8) and cylic ether 76
as the sole product, in the latter (Table 2, entry 9); the
ring-opened intermediates 68 and 69, respectively, could
not be isolated. On the other hand, the reaction of
cyclohexenyl acetate 17 with either phenol 27 or p-cresol
29 stopped at the stage of the o-substituted product 71
or 72, respectively (Table 2, entries 13-15), accompanied
by a small amount of bis-allylated byproducts, as revealed
by GCMS.
Of the five-membered ring allylic substrates 18 and
19, the former gave almost exclusively elimination prod-
ucts, whereas the latter followed the pattern of its
cyclohexene-derived counterparts (Scheme 10). Thus,
reaction of 19 with anisole afforded mainly p-substituted
product 77 (Table 2, entry 16), while reaction with phenol
gave rise to o-substituted product 78 (Table 2, entry 17);
in both cases, small amounts of bis-allylated byproducts
were detected. However, the isolated yields were lower
than those in the cyclohexene series, owing to the larger
proportion of competing elimination of the allylic sub-
strate. The doubly activated aromatics 31 and 32 gave
acceptable yields of the corresponding substitution prod-
ucts 79 and 80, respectively (Table 2, entries 18 and 19).
The aliphatic allylic acetate 20 (Scheme 11) turned out
to be less efficient than the other members of the series
(7-19), mainly due to preferential elimination. Never-
theless, the reaction with anisole furnished the p-sub-

2756 J . Org. Chem., Vol. 64, No. 8, 1999
Malkov et al.
Sch em e 11
Sch em e 13
Sch em e 12
allowing an overlap of π and σ* orbitals in the transition
state at low energy cost, is the prerequisite for the
reaction to occur readily.
The epimeric pair of bicyclic allylic acetates 24 and 25,
first introduced by Fiaud,23 has previously been employed
to establish the steric course of Pd(0)- and Mo(0)-
catalyzed allylic substitution.5a,9,23 The advantage of this
system is the steric bias, which renders the endo-face
inaccessible by both the catalyst and the nucleophile.5a,b,9,23
In agreement with the previously observed reactivity
toward Mo(0)9 and Mo(II),12 exo-acetate 24 turned out to
react readily with either phenol or anisole, affording the
respective exo-products 92 and 93 (Table 2, entries 28
and 29). Note, again, the selective ortho-substitution for
phenol (92) and the para-attachment for anisole (93). The
endo-epimer 25 also furnished 93 on reaction with anisole
(Table 2, entry 30), although in a somewhat slower
process (6 h vs 1 h; compare entries 28 and 30), which is
in agreement with the previously observed reactivity
toward silyl enol ethers.12
The reaction of the enantiomerically pure allylic ac-
etate (R)-(+)-75b with anisole produced racemic 37 in
excellent yield (Table 1, entry 9), demonstrating the
nonstereospecific nature of these Mo(II)-catalyzed ally-
lation reactions; the role of Mo(II) catalyst can thus be
defined as that of a very selective Lewis acid, which is
in line with our previous observations.12
stitution product 81 in 24% yield (Table 2, entry 20). With
phenol, an initial formation of 83 was observed by TLC,
followed by cyclization to produce the benzopyran deriva-
tive 85 (Table 2, entry 21). Prenyl acetate 21 exhibited
similar behavior, giving 82 with anisole (Table 2, entry
22), whereas the cyclic product 86 resulted from the
reaction with phenol (Table 2, entry 23); the ring-opened
intermediate 84 could not be isolated. Notably higher
yields were obtained when the allylic isomer 22 was
utilized as electrophile (Table 2, entries 24 and 25).
The reaction of 15 with the furan derivative 34 pro-
ceeded readily, furnishing the expected substitution
product 87 in high yield (Scheme 12; Table 2, entry 6),
and so did the reactions of 15 and 16 with N-methylindole
(36), which afforded the â-substituted indole derivatives
88 and 89, respectively (Table 2, entries 7 and 10).
Ster eoch em istr y. To establish the stereochemistry of
the allylation process with respect to the allylic electro-
phile, we first investigated the reactivity of allylic acetate
23 (Scheme 13). Its reaction with phenol catalyzed by
complex B proceeded readily at ambient temperature,
giving a 90:10 mixture of o- and p-isomers 90 and 91
(Table 2, entry 26), separated by semipreparative HPLC.
1H NMR spectroscopy revealed that the products were
contaminated by the corresponding cis-isomers (the trans/
cis ratios were 81:19 for 90 and 75:25 for 91), which could
not be separated. The same reaction catalyzed by complex
C also afforded a 90:10 mixture of 90 and 91 (Table 2,
entry 27), in which the content of the cis-isomer was
similar to the later case (75:25). In contrast to this ready
reaction, the cis-epimer of 23 reacted sluggishly, giving
mainly elimination products. Apparently, the pseudoaxial
disposition of the leaving group in the trans-epimer 23,
Mech a n ist ic Con sid er a t ion s. The Pd(0)-catalyzed
reaction of ethyl cinnamyl carbonate 4 with â-naphthol
(Scheme 2) has been shown by Sinou11 to give first the
O-allylated kinetic product 5, which is rearranged at
higher temperature to the thermodynamic C-alkylated
product 6. Although the latter rearrangement could be
conjectured as occurring via Claisen rearrangement
(Scheme 14), Sinou has demonstrated that this is not the
(23) Fiaud, J .-C.; Legros, J .-Y. J . Org. Chem. 1987, 52, 1907.

Molybdenum(II)-Catalyzed Allylation
J . Org. Chem., Vol. 64, No. 8, 1999 2757
Sch em e 14
overall retention (via inv-inv mechanism) for O-allylation,
using the cis-epimer of 23.11,25 With this stereochemistry
in mind, we have reacted allylic carbonate (R)-(+)-101
(synthesized from the corresponding alcohol of 95% ee5b)
with phenol to obtain (R)-(+)-102 (75%).26,27 Similarly,
the Pd(0)-catalyzed reaction of (R)-(+)-101 with â-naph-
thol afforded the naphthoxy derivative (R)-(+)-104 (86%).26
Whereas the O-allylated derivatives (+)-102 and (+)-104
proved inert to Pd catalysts, their rearrangement to the
respective C-allylated products 38/41 (1:1) and 105 was
accomplished on treatment with a catalytic amount of
complex B (room temperature, 20 or 8 h). However, the
latter transformations turned out to be much slower than
the direct C-C bond-forming allylation (note that 30 min
is required for the reaction of 7 with PhOH: Table 1, entry
2), and the respective products 38/41 and 105 proved to
be racemic. Moreover, free phenol and â-naphthol (∼5%),
respectively, were detected in the crude reaction mixtures
by GCMS. Similar results were obtained with other Lewis
acids, such as (TfO)3Yb (rt, overnight). An entirely dif-
ferent picture was obtained when Eu(fod)3 was employed
as the Lewis acid. In consonance with Trost’s findings,
the product of Claisen rearrangement 103 (80 °C, 12 h
in dichloroethane; ∼75% conversion)28 was formed and
proved to be of 76% ee as revealed by HPLC on Chiralcel
OD-H column. The naphthyl derivative 104 reacted sim-
ilarly with Eu(fod)3 to afford the corresponding product
of Claisen rearrangement 106 (80 °C, 12 h in dichloro-
ethane; >95% conversion; 82% ee). Each of 103 and 106
was obtained as a ∼4:1 mixture of trans/ cis-isomers.
In another experiment (Scheme 17), cyclohexenyl phen-
yl ether 107, synthesized from cyclohex-1-en-2-ol and
phenol via the Mitsunobu reaction (DEAD, Ph3P; 77%),29
was converted into the C-alkylated ortho-product 71
(36%) and its p-isomer (10%) on treatment with B (5 mol
%); unreacted 107 (15%), free phenol (∼5%), and some
elimination products were also detected in the crude
reaction mixture. Again, the reaction was much slower
than the direct allylation of phenol with cyclohexenyl ace-
tate 17 (20 h vs 30 min), lending more credence to the
above finding that the Mo(II)-catalyzed transformation
of the allyl ether into the C-allylated product is an inter-
rather than intramolecular process.
Sch em e 15
case, since the Claisen rearrangement should give 96
rather than 6. According to his interpretation, ArO serves
as a leaving group in the presence of Pd(0), which allows
for generation of the corresponding π-allyl complex 95
together with naphthoxide (94), whose recombination
eventually leads to 6. Interestingly, this reactivity ap-
pears to be confined to naphthoxy derivatives; the cor-
responding phenoxy systems were inert under the same
conditions.
Recently, Trost has also examined the rearrangements
of arylallyl ethers, such as (R)-99, obtained on the
reaction of racemic allylic carbonate 97 with phenol 98,
catalyzed by a chiral Pd(0) complex (Scheme 15). Whereas
Pd catalysts proved ineffective in his systems, he found
that (R)-99 underwent Claisen rearrangement by the
action of Eu(fod)3 at 50 °C; formation of (S)-100 as the
main product is compatible with the involvement of a
chairlike transition state.24
In light of these reports, it was of interest to elucidate
the mechanism of our Mo(II)-catalyzed C-C bond-form-
ing reactions. Although we were unable to intercept the
O-allylation product, its formation as a short-lived in-
termediate could not be a priori excluded. Furthermore,
the Mo(II)-catalyzed reaction with MeOH as a prototype
O-nucleophile (7 + MeOH f 9; Scheme 4) has been
shown by us to occur with complete racemization.12
Hence, if the O-allylated species were the intermediate,
racemization would occur in the first step, leaving the
question of the stereochemistry of the putative rear-
rangement to the C-allylated product open. To address
these issues, an enantiopure O-allyl derivative of known
configuration was required. Sinou has demonstrated an
The above results rule out the involvement of Claisen
rearrangement in the Mo(II)-catalyzed allylation of free
phenols and demonstrate that, although some of the final
product may arise from the initially generated O-ally-
(25) Note that the stereochemical course of the O-allylation could
not be established with the Trost system24 as the carbonate 97 forms
a meso-π-allyl complex.
(26) The (R)-configuration for (+)-102 ([R]D +81.7; c 2.1 in CHCl3)
and (+)-104 ([R]D +233.3; c 2.0 in CHCl3) is assumed in view of the
double inversion mechanism demonstrated for this type of reaction by
Sinou11 but not rigorously proven. Note that other O-nucleophiles are
also known to react via the inv-inv mechanism; for an overview, see
the references list in ref 5b. The ee for the latter aryloxy compounds
could not be determined since their maximum optical rotations are
unknown and we failed to separate the enantiomers of the correspond-
ing racemates on the available chiral columns.
(27) Interestingly, the Mitsunobu reaction of (()-4-phenyl-but-3-en-
2-ol with PhOH (DEAD, Ph3P, THF, rt, 4 h) gave a 67:33 mixture of
(()-102 and its allylic isomer.
(28) The spectral characteristics for (R)-103 are identical to those
reported for the corresponding racemate. The (R)-configuration for both
103 and 106 is assumed in view of the prevailing chairlike transition
state for the Claisen rearrangement, proposed by Trost.24 For (()-103,
see: Albergola, A.; Gonzalez-Ortega, A.; Pedrosa, R.; Vicente, M.
Synthesis 1984, 238.
(29) For review, see: (a) Mitsunobu, O. Synthesis 1981, 1. (b) Shull,
B. K.; Sakai, T.; Nichols, J . B.; Koreeda, M. J . Org. Chem. 1997, 62,
8294.
(24) Trost, B. M.; Toste, F. D. J . Am. Chem. Soc. 1998, 120, 815. (b)
Trost, B. M.; Toste, F. D. J . Am. Chem. Soc. 1998, 120, 9074.

2758 J . Org. Chem., Vol. 64, No. 8, 1999
Malkov et al.
Sch em e 16
F igu r e 1. Orbital interactions between the allylic cations
derived from 15 (R ) Me) or 17 (R ) H) with 26 (R′ ) Me) or
27 (R′ ) H).
kylation rather than via the O-allylated intermediate, so
that the difference between the regioselectivity of anisole
vs phenol must, indeed, originate from another effect.
To shed light on the differences in regioselectivity of
the reactions of allylic substrates, such as 15, with
PhOMe (26) vs PhOH (27), let us consider the HOMO-
LUMO interactions (Figure 1). In the reaction of PhOH
with 15, the HOMO of PhOH should interact with the
LUMO of the allylic cation derived from 15 (R ) Me).
For bond formation between the ortho-carbon of PhOH
(R′ ) H) and the less substituted terminus (1) of the latter
cation (I), an additional stabilizing interaction can be
identified between the orbital located on the oxygen atom
of PhOH and the 3-position of the cation. The formation
of the para-isomer can either occur without the secondary
interactions (III) or, perhaps, via II, in which the bond-
forming interaction between the p-carbon of PhOH and
the less substituted carbon of the cation (C-1) is supple-
mented by the stabilizing interaction of the ortho-orbital
of PhOH with the orbital in the 3-position of the cation.
Since the negative charge in PhOH is mainly residing
on the oxygen, the O-C interaction in I should be more
significant than the C-C interaction in II, which is in
agreement with the preferential formation of the ortho-
isomer. Note that considering purely Coulombic interac-
tions would lead to the same conclusions. A dramatically
different scenario is encountered in the reaction of 15
with PhOMe, where severe eclipsed interaction between
the two methyls would render the transition state I (R
) R′ ) Me) much higher in energy, so that an alternative
(II or III) becomes favored. The reactivity of 17 lends
further credence to this model: in this instance, the
repulsive interaction in the transition state I is absent
(R ) H), allowing the formation of the ortho-substituted
product, which is in perfect agreement with the experi-
ment that gives a ∼3:2 p/o-ratio (Table 2, entries 11 and
12).
Sch em e 17
lated intermediate, this is not the main reaction channel
for the catalytic C-allylation. The stereospecific Claisen
rearrangement of O-allyl derivatives, reported by Trost,24
appears to be unique to Eu(III); other Lewis-acid cata-
lysts, such as Mo(II) or Yb(III), drive the reaction toward
dissociation followed by recombination.
Or th o-/P a r a -Selectivity. The stereochemical inves-
tigation pointed to the Mo(II)-initiated ionization of the
allylic acetate to generate the corresponding allylic
cation, which then attacks the electron-rich aromatic
ring. This scenario should lead to the classical distribu-
tion of ortho- and para-isomers. However, anisole exhib-
ited almost exclusive preference for the para-substitution
in most reactions (Table 1, entries 1, 9, and 10; Table 2,
entries 1, 2, 16, 20, 22, 24, 28, and 30) except in one case
(Table 2, entries 11 and 12). Phenol, on the other hand,
exhibited high preference for the formation of ortho-
isomers, especially with cyclic allylic acetates (Table 2,
entries 3, 4, 8, 13, 14, 17, 21, 23, 25, 26, and 29), whereas
para-substitution was favored in the case of the cinnamyl
system (Table 1, entries 2 and 11). Since steric effects
alone, i.e., OCH3 vs OH, can hardly be taken responsible
for such a dramatic change of regioselectivity, there must
be other factors operating in these reactions. Note that
the metal is apparently not involved in coordination of
the allylic cation via an η3-complex as evidenced by
scrambling of the original stereochemical information
(vide supra). Moreover, phenol, a potentially bidentate
nucleophile, has been shown to also react by direct C-al-
A similar analysis can be applied to the reaction of the
cinnamyl electrophile 8 with the same pair of nucleo-
philes (Figure 2). The transition states IV and V are
apparently less stabilized by additional interactions than
their counterparts I and II, since the charge in the
benzylic position (3) is further delocalized to the aromatic
ring of the cinnamyl unit. Moreover, a steric clash
between OH/OMe and the Ph group can be identified in
IV. As a result, transition state VI can be regarded as
more likely, which is in agreement with the experimen-

Molybdenum(II)-Catalyzed Allylation
J . Org. Chem., Vol. 64, No. 8, 1999 2759
matics, catalyzed by the readily available Mo(II) com-
plexes [Mo(CO4Br2]2 (B) or Mo(CO)3(MeCN)2(SnCl3)Cl
(C), which have not been used in catalytic chemistry
before. The para-selectivity, observed with anisole (26)
and its congeners, is remarkable. Since selected het-
eroaromatics, such as the furan and indole derivatives
34 and 36, undergo the reaction as easily as other
aromatics, complexes B and C are likely to become a
valuable addition to the menu of the Friedel-Crafts-type
catalysts for allylation of aromatics. The salient features
of our method are the low catalyst loading (e2 mol %)
and the mild conditions (room temperature or lower for
30 min - 2 h). In the overall reaction outcome, the
reactivity of catalysts B and C seems to parallel that of
LiCo(B9C2H11)2 (lithium cobalt bis(dicarbollide)) and re-
lated Li+ reagents.34
F igu r e 2. Orbital interactions between the allylic cations
derived from 8 with 26 (R ) Me) or 27 (R ) H).
Exp er im en ta l Section
Sch em e 18
Gen er a l Meth od s. Melting points were determined on a
Kofler block and are uncorrected. The NMR spectra were
1
recorded in CDCl3, H at 250 MHz and 13C at 62.9 MHz with
chloroform-d1 (δ 7.26, 1H; δ 77.0, 13C) as internal standard;
2D-techniques were used to establish the structures and to
assign the signals. The IR spectra were recorded for a thin
film between KBr plates unless otherwise stated. The mass
spectra (EI and/or CI) were measured on a dual sector mass
spectrometer using direct inlet and the lowest temperature
enabling evaporation. The GC-MS analysis was performed
with RSL-150 column (25m × 0.25 mm). Chiral HPLC analy-
ses were carried out on Chiralpak AD (Daicel) and Chiracel
OD (Daicel) columns with a 10 mm guard column (silica), using
UV detection at 254 nm. All reactions were performed under
an atmosphere of dry, oxygen-free nitrogen in oven-dried
glassware. The catalysts were prepared by literature meth-
ods: [Mo(CO)4Br2]2 (B);12,15 Mo(CO)3(MeCN)2(SnCl3)Cl (C).12,16
Cinnamyl acetate (8) was purchased from Lancaster Synthesis
Ltd. Other allylic acetates are known compounds35 and were
prepared by stirring the corresponding allylic alcohols with a
mixture of acetic anhydride and triethylamine and a catalytic
amount of (dimethylamino)pyridine in diethyl ether. Carbon-
ate (R)-(+)-10136 was prepared according to the literature
procedure11 from the corresponding alcohol5b (95% ee). All
aromatic and heteroaromatic compounds were purchased and
used without further purification. Some of the products are
known compounds.37 Yields are given for isolated product
showing one spot on a TLC plate and no impurities detectable
in the NMR spectrum.
tally observed shift of the preference to the p-substitution
even for PhOH (Table 1, entries 1, 2, and 9-11).
Ep ilogu e
While this work was in progress, two papers appeared
reporting on the transition metal-catalyzed Friedel-
Crafts-type allylation of aromatics, such as toluene,
xylene, and anisole, with allylic esters, chlorides, or
alcohols.30,31 However, neither Mo(CO)6 (10 mol %)30 nor
Cp*RuCl(SPri)-Ru(OH2)(SPri)Cp* (5 mol %),31 employed
as catalysts, was as selective as our Mo(II) complexes and
the reaction condition were rather harsh (typically 80-
140 °C for 6-72 h).
In another recent paper, Mo(CO)6 has been shown to
catalyze the conversion of prenyl phenyl ether (108) (110
°C for 55 h) into dimethylchromane (86) (65%); interest-
ingly, free phenol (5-10%) was detected in the crude
reaction mixture (Scheme 18).32 In light of our findings,
one can envisage the following mechanism: on reaction
with the catalyst, the PhO- group departs with concomi-
tant formation of π-prenyl complex 110, which then
recombines with the phenoxide (109) to give the C-
allylated intermediate 111, whose 6(O)n-endo-Trig cy-
clization,33 analogous to that described in Scheme 9,
affords the final chroman 86 by obeying the Markovnikov,
rather than Baldwin, rule.
Gen er a l P r oced u r e for Allylic Su bstitu tion Usin g
Ca ta lysts B or C. To a stirred solution of an allylic acetate
(1 equiv) and a nucleophile (1.1-1.3 equiv) in CH2Cl2 (5 mL)
at room temperature was added 2-5 mol % of the catalyst (B
(33) For the notation and detailed discussion of related cyclizations,
see, e.g.: (a) Kocˇovsky´, P.; Stieborova´, I. J . Chem. Soc., Perkin Trans.
1 1987, 1969. (b) Kocˇovsky´, P.; Pour, M. J . Org. Chem. 1990, 55, 5580.
(34) Grieco, P. A.; DuBay, W. J .; Todd, L. J . Tetrahedron Lett. 1996,
37, 8707. (b) Henry, K. J .; Grieco, P. A. J . Chem. Soc., Chem. Commun.
1993, 510.
(35) Allylic acetates references are as follows. 7: (a) Goering, H. L.;
Seits, E. P., J r.; Tseng, C. C. J . Org. Chem. 1981, 46, 5304. 15: (b)
Ishida, T.; Asakawa, Y.; Okano, M.; Aratani, T. Tetrahedron Lett. 1977,
18, 2437. 16 and 17: (c) Lessard, J .; Tan, P. V. M.; Martino, R.; Sanders,
J . K. Can. J . Chem. 1977, 55, 1015. 18: (d) Masatoshi, A.; Bull. Chem.
Soc. J pn. 1990, 63, 721. (e) Shono, T.; Ikeda, A. J . Am. Chem. Soc.
1972, 94, 7892. 19: (f) Hansson, S.; Heumann, A.; Rein, T.; A° kermark,
B. J . Org. Chem. 1990, 55, 975. 20: (g) Michejda, C. J .; Comnick R. W.
J . Org. Chem. 1975, 40, 1046. 21: (h) Suga, K.; Watanabe, S.; Hijikata,
K. Aust. J . Chem. 1971, 24, 197. 22: (i) Bergstrom, D. E.; Ruth, J . L.;
Warwick, P. J . Org. Chem. 1981, 46, 1432. 23: (j) Trost, B.; Verhoeven,
T. R. J . Am. Chem. Soc. 1980, 102, 4730. 24 and 25: ref 3g.
Enantiomerically pure acetate (R)-(+)-7 was obtained by acetylation
of the enantiomerically pure alcohol which, in turn, was obtained from
the racemate by Sharpless epoxidation in kinetic resolution mode and
had [R]D +24.5 (c 2.5, CHCl3).5b,12
Con clu sion s
We have developed a new, extremely mild method for
C-allylation of electron-rich aromatics and heteroaro-
(30) Shimizu, I.; Sakamoto, T.; Kawaragi, S.; Maruyama, Y.; Yama-
moto, A. Chem. Lett. 1997, 137.
(31) Nishibayashi, Y.; Yamanashi, M.; Takagi, Y.; Hidai, M. J . Chem.
Soc., Chem. Commun. 1997, 859.
(32) Bernard, A. M.; Cocco, M. T.; Onnis, V.; Piras, P. P. Synthesis
1997, 41. (b) Bernard, A. M.; Cocco, M. T.; Onnis, V.; Piras, P. P.
Synthesis 1998, 256.
(36) Zhou, B.; Xu, Y. J . Org. Chem. 1988, 53, 4419.

2760 J . Org. Chem., Vol. 64, No. 8, 1999
Malkov et al.
or C) in one portion. The mixture was stirred under nitrogen
until the reaction was complete (as evidenced by TLC), then
diluted with ether (20 mL), and washed successively with 5%
aqueous NaHCO3 and water. The organic phase was dried with
MgSO4, and the solvent was evaporated under reduced pres-
sure. The crude product was purified by flash chromatography
on silica gel (15 × 2 cm) with a 9:1 hexanes-ethyl acetate
mixture as an eluent.
1-P h en yl-3-(4′-m eth oxyp h en yl)-1-bu ten e (37). Acetate
7 (100 mg, 0.53 mmol) was reacted with anisole (26) (70 mg,
0.65 mmol) in the presence of catalyst B (5 mol %) in CH2Cl2
(5 mL) to give 37 (114 mg, 91%) as a colorless oil (Table 1,
entry 1): 1H NMR δ 1.43 (d, J ) 6.9 Hz, 3 H, Me), 3.58 (m, 1
H, 3-H), 3.76 (s, 3 H, OMe), 6.37 (m, 2 H, 1-H, 2-H), 6.85 (d, J
) 8.8 Hz, 2 H, 3′-H, 5′-H), 7.17 (d, J ) 8.8 Hz, 2 H, 2′-H, 6′-
H), 7.20-7.36 (m, 5 H, Ph); 13C NMR δ 21.3 (Me), 41.7 (3-
CH), 55.2 (OMe), 113.8 (3′,5′-CH), 126.1, 127.0, 128.2, 128.3,
128.5, 135.6 (1-CH), 137.6 and 137.7 (1′-C and 1′′-C), 158.0
(4′-C); MS (EI) m/z (%) 238 (71, M•+), 223 (100).
1-P h en yl-3-(4′-h ydr oxyph en yl)-1-bu ten e (38)an d 1-P h en -
yl-3-(2′-h yd r oxyp h en yl)-1-bu ten e (41). Acetate 7 (100 mg,
0.53 mmol) was reacted with phenol (27) (60 mg. 0.64 mmol)
in the presence of catalyst B (5 mol %) in CH2Cl2 (5 mL) to
afford an 18:82 mixture of 38 and 41 (111 mg, 94%) as a
colorless oil (Table 1, entry 2): MS (EI) m/z (%) 224 (73, M•+),
209 (100). 38: 1H NMR δ (measured in a mixture with the
ortho-isomer) 1.41 (d, J ) 6.9 Hz, 3 H, Me), 3.56 (m, 1 H, 3-H),
5.08 (br s, 1 H, OH), 6.36 (m, 2H, 1-H, 2-H), 6.75 (d, J ) 8.5
Hz, 2 H, 3′-H, 5′-H), 7.11 (d, J ) 8.5 Hz, 2 H, 2′-H, 6′-H), 7.17-
7.36 (m, 5 H, Ph); 13C NMR δ 21.8 (Me), 42.1 (3-CH), 115.8
(3′,5′-CH), 126.6, 127.5, 128.8, 129.0, 130.2, 136.1 (1-CH), 138.1
and 138.3 (1′, 1′′-C), 154.3 (4′-C). 41: 1H NMR δ (measured in
a mixture with the para-isomer) 1.47 (d, J ) 7.0 Hz, 3 H, Me),
3.88 (m, 3 H, 3-H), 5.08 (br s, 1 H, OH), 6.47 (m, 2 H, 1-H,
2-H), 6.87-7.4 (m, 2 H, 4′-H, 6′-H).
1-P h en yl-3-(4′-h yd r oxyp h en yl)-1-p r op en e (40)37b,c a n d
1-P h en yl-3-(2′-h yd r oxy-p h en yl)-1-p r op en e (42).37c Acetate
8 (100 mg, 0.57 mmol) was reacted with phenol (27) (60 mg,
0.64 mmol) in the presence of catalyst B (5 mol %) in CH2Cl2
(5 mL) to produce a 17:83 mixture of 40 and 42 (85 mg, 71%)
as a colorless oil (Table 1, entry 11): MS (EI) m/z (%) 210 (100,
1
M•+). 40: H NMR δ (measured in a mixture with the ortho-
isomer) 3.46 (d, J ) 6.0 Hz, 2 H, 3-H), 5.01 (s, 1 H, OH), 6.31
(dt, J ) 15.9, 6.0 Hz, 1 H, 2-H), 6.42 (d, J ) 16.0 Hz, 1 H,
1-H), 6.84 (d, J ) 8.5 Hz, 2 H, 3′-H, 5′-H), 7.13 (d, J ) 8.5 Hz,
2 H, 2′-H, 6′-H), 7.17-7.35 (m, 5 H, Ph); 13C NMR δ 38.9 (3-
CH2), 115.8 (3′,5′-CH), 126.6, 127.5, 129.0, 130.1, 130.3, 131.2
1
(1-CH), 132.8 and 138.0 (1′-C and 1′′-C), 154.3 (4′-C). 42: H
NMR δ (measured in a mixture with the para-isomer) 3.57 (d,
J ) 6.0 Hz, 2 H, 3-H), 4.93 (s, 1 H, OH), 6.38 (dt, J ) 15.8 and
6.0 Hz, 1 H, 2-H), 6.51 (d, J ) 16.0 Hz, 1 H, 1-H), 6.81 (d, J )
8.2 Hz, 6′-H), 6.88 (t, J ) 7.2, 1 H, 4′-H), 7.11-7.37 (m; 7H,
3′-H, 5′-H, 2′′-H, 6′′-H).
1-P h en yl-3-(2′-m eth oxy-5′-m eth ylph en yl)-1-bu ten e (43).
Acetate 7 (100 mg, 0.53 mmol) was reacted with 4-methylani-
sole (28) (85 mg, 0.70 mmol) in the presence of catalyst B (5
mol %) in CH2Cl2 (5 mL) to afford 43 (81 mg, 61%) as a
colorless oil (Table 1, entry 3): 1H NMR δ 1.40 (d, J ) 6.9 Hz,
3 H, 4-Me), 2.26 (s, 3 H, 5′-Me), 3.79 (s, 3 H, OMe), 4.06 (m, 1
H, 3-H), 6.41 (m, 2 H, 1-H, 2-H), 6.75 (d, J ) 8.8 Hz, 1 H,
3′-H), 7.03 (m, 2 H, 4′-H, 6′-H), 7.12-7.40 (m, 5 H, Ph); 13C
NMR δ 20.5 (Me), 21.0 (Me), 35.6 (3-CH), 56.1 (OMe), 111.1
(CH), 126.5 (2′,6′-CH), 127.2 (CH), 127.8 (CH), 128.5 (CH),
128.7 (CH), 128.8 (3′,5′-CH), 130.2 (C), 134.3 (C), 135.5(CH),
138.4 (C), 158.0 (2′′-C); MS (EI) m/z (%) 252 (89, M•+), 237
(100).
1-P h en yl-3-(2′-h ydr oxy-5′-m eth ylp h en yl)-1-bu ten e (44).
Acetate 7 (100 mg, 0.53 mmol) was reacted with p-cresol (29)
(70 mg, 0.65 mmol) in the presence of catalyst B (5 mol %) in
CH2Cl2 (5 mL) to furnish 44 (70 mg, 56%) as a colorless oil
(Table 1, entry 4): 1H NMR δ 1.46 (d, J ) 6.9 Hz, 3 H, 4-Me),
2.26 (s, 3 H, 5′-Me), 3.86 (qd; J ) 6.9, 5.0 Hz, 1 H, 3-H), 5.01
(s, 1 H, OH), 6.40 (dd, J ) 16.0, 5.0 Hz, 1 H, 2-H), 6.49 (d, J
) 16.0 Hz, 1 H, 1-H), 6.67 (d, J ) 8.2 Hz, 1 H, 3′-H), 6.89 (dd,
J ) 8.2, 1.9 Hz, 1 H, 4′-H), 6.98 (d, J ) 1.9 Hz, 1 H, 6′-H),
7.15-7.37 (m, 5 H, Ph); MS (EI) m/z (%) 238 (85, M•+), 91 (100).
1-P h en yl-3-(2′-h ydr oxy-5′-m eth oxyph en yl)-1-bu ten e (45)
an d 2,5-Bis(1′-ph en yl-1′-bu ten -3′-yl)-4-m eth oxyph en ol (48).
Acetate 7 (100 mg, 0.53 mmol) was reacted with 4-methoxy-
phenol (30) (90 mg, 0.72 mmol) in the presence of catalyst B
(5 mol %) in CH2Cl2 (5 mL) to give a 34:66 mixture of 45 and
48 (81 mg, 61%) as a colorless oil (Table 1, entry 5). The two
compounds were separated by column chromatography on
silica (20 × 2.5 cm) with a hexanes-ethyl acetate mixture (9:
1) as an eluent. The slower moving component was identified
as 45: 1H NMR δ 1.47 (d, J ) 7.2 Hz, 3 H, 4-Me), 3.76 (s, 3 H,
OMe), 3.87 (m, 1 H, 3-H), 4.84 (s, 1 H, OH), 6.39 (dd, J ) 16.0,
5.7 Hz, 1 H, 2-H), 6.49 (d, J ) 16.3 Hz, 1 H, 1-H), 6.66 (dd, J
) 8.8, 1.9 Hz, 1 H, 4′-H), 6.74 (d; J ) 8.8 Hz, 1 H, 3′-H), 6.78
(d, J ) 1.9 Hz, 1 H, 6′-H), 7.15-7.37 (m, 5 H, Ph); MS (EI)
m/z (%) 254 (58, M•+), 150 (100). The faster moving component
was identified as 48: 1H NMR (recorded for a ∼1:1 mixture of
diastereoisomers) δ 1.38 and 1.47 (2 × d, J ) 7.2 and 6.9 Hz,
respectively, 2 × 3 H, 4′-Me and 4′′-Me), 3.80 (s, 3 H, OMe),
3.86 and 4.02 (2 × m, 2 × 1 H, 3′-H and 3′′-H), 4.81 (s, 1 H,
OH), 6.36-6.54 (m, 4 H, 1′-H, 1′′-H, 2′-H, 2′′-H), 6.61 and 6.71
(2 × s, 2 × 1 H, 3-H and 6-H), 7.16-7.37 (m, 10 H, 2 × Ph);
MS (EI) m/z (%) 384 (62, M•+), 369 (100).
1-P h en yl-3-(4′-m eth oxyp h en yl)-1-p r op en e (39).37a,b Ac-
etate 8 (100 mg, 0.57 mmol) was reacted with anisole (26) (70
mg, 0.65 mmol) in the presence of catalyst B (5 mol %) in CH2-
Cl2 (5 mL) to furnish 39 (87 mg, 68%) as a colorless oil (Table
1, entry 10): 1H NMR δ 3.46 (d, J ) 6.0 Hz, 2 H, 3-H), 3.76 (s,
3 H, OMe), 6.31 (dt, J ) 15.9, 6.0 Hz, 1 H, 2-H), 6.42 (d, J )
16.0 Hz, 1 H, 1-H) 6.84 (d, J ) 8.5 Hz, 2 H, 3′-H, 5′-H), 7.13
(d, J ) 8.5 Hz, 2 H, 2′-H, 6′-H), 7.17-7.35 (m, 5 H, Ph), 13C
NMR δ 38.9 (3-CH2), 55.7 (OMe), 114.4 (3′,5′-CH), 126.6, 127.5,
129.0, 130.1, 130.2, 131.2 (1-CH), 132.6 and 138.0 (1′-C and
1′′-C), 158.6 (4′-C); MS (EI) m/z (%) 224 (100, M•+).
(37) Previously described products of the allylation are the following.
39: (a) Hase, T. Acta Chem. Scand. 1969, 23, 2403. (b) Wenkert, E.;
Fernandes, J . B.; Michelott, E. L.; Swindell, C. S. Synthesis 1983, 701.
40: ref 37b and (c) Dewar, M. J . S.; Nahlovsky, B. D. J . Am. Chem.
Soc. 1974, 96, 460. 42: ref 37c. 46: (d). Viktorova, E. A.; Shujkin, N.
I.; Karakhanov, E. A. Izv. Akad. Nauk SSSR, Ser Khim 1964, 2216.
47: (e) J urd, L.; Stevens, K.; Manners, G. Tetrahedron 1973, 29, 2347.
(f) J imenez, M. C.; Leal, P.; Miranda, M. A.; Tormos, R. J . Org. Chem.
1995, 60, 3243. 55: (g) Tarnopol’skii, Yu. I.; Belov, V. N. Khim.
Geterotsikl. Soedin. 1967, 10. 65: (h) Kamigata, N.; Satoh, H.; Kondoh,
T.; Kameyama, M. Bull. Chem. Soc. J pn. 1988, 61, 3575. 70: (i) Birch,
A. J .; Nadamuni, G. J . Chem. Soc., Perkin Trans. 1 1974, 545. 71: (j)
Fra´ter, G.; Schmid, H. Helv. Chim. Acta 1967, 50, 255. 72: (k)
Majumdar, K. C.; Kundu, A. K. Can. J . Chem. 1995, 73, 1727. 73: (l)
Kuhn, R.; Weiser, D. Chem. Ber. 1955, 88, 1601 and 1603. 77: ref 37h.
78: ref 37i. 81: (m) Tzeng, Y.-L.; Yang, P.-F.; Mei, N.-W.; Yuan, T.-
M.; Yu, C.-C.; Luh, T.-Y. J . Org. Chem. 1991, 56, 5289. 82: (n) Gnichtel,
H.; Beier, M. Liebigs Ann. Chem. 1981, 312. (o) Zimmerman, H. E.;
Swafford, R. L. J . Org. Chem. 1984, 49, 3069. (p) Hixson, S. S.; Gallucci,
C. R. J . Org. Chem. 1988, 53, 2713. (q) Del Vale, L. Stille, J . K.;
Hegedus, L. S. J . Org. Chem. 1990, 55, 3019. (r) Tofeva M. M.; Richard,
J . P. J . Am. Chem. Soc. 1996, 118, 11434. (s) Robbins, R. J .;
Ramamurthy, V. Chem. Commun. 1997, 1071. 83: (t) Aniol, M.; Lusiak,
P.; Wawrzenczyk, Cz. Heterocycles 1994, 38, 991. 84: ref 37t and (u)
Hurd, C. D.; Hoffman, W. A. J . Org. Chem. 1940, 5, 212. (v) Bader, A.
R. J . Am. Chem. Soc. 1956, 78, 1709. (w) Bader, A. R.; Bean, W. C. J .
Am. Chem. Soc. 1958, 80, 3073. (x) Birch, A. J .; Maung, M.; Pelter, A.
Aust. J . Chem. 1969, 72, 1923. (y) Hlubucek, J .; Ritchie, E.; Taylor,
W. C. Aust. J . Chem. 1971, 24, 2355. (z) Dewhirst, K. C.; Rust, F. F. J .
Org. Chem. 1963, 28, 798. (aa) Alberola, A.; Ortega, A. G.; Pedrosa,
R.; Bragado, J . L. P.; Amo-Rodriquez, J . F. J . Chem. Soc., Perkin Trans.
1 1983, 1209. 85: ref 37t. 86: ref 37h,t. 103: (bb) Alberola, A.;
Gonzalez-Ortega, A.; Pedrosa, R.; Vincente, M. Synthesis 1984, 238.
1-P h en yl-3-(2′-m et h oxy-5′-m et h ylp h en yl)-1-p r op en e
(46).37d Acetate 8 (100 mg, 0.57 mmol) was reacted with
4-methylanisole (28) (85 mg, 0.70 mmol) in the presence of
catalyst B (2 mol %) in CH2Cl2 (5 mL) to produce 46 (40 mg,
30%) as a colorless oil (Table 1, entry 12): 1H NMR δ 2.26 (s,
3 H, 5′-Me), 3.50 (d, J ) 5.5 Hz, 2 H, 3-H), 3.81 (s, 3 H, OMe),
6.34 (dt, J ) 15.7, 5.6 Hz, 1 H, 2-H), 6.43 (d, J ) 15.7 Hz, 1 H,
1-H), 6.76 (d, J ) 8.8 Hz, 1 H, 3′-H), 6.98 (m, 2 H, 4′-H, 6′-H),
7.14-7.37 (m, 5 H, Ph); MS (EI) m/z (%) 238 (100, M•+).
1-P h e n y l-3-(2′-h y d r o x y -5′-m e t h o x y p h e n y l)-1-p r o -
p en e (47)37e,f a n d 2,5-Bis-(1′-p h en yl-1′-bu ten -3′-yl)-4-m eth -
oxyp h en ol (49). Acetate 8 (100 mg, 0.57 mmol) was reacted

Molybdenum(II)-Catalyzed Allylation
J . Org. Chem., Vol. 64, No. 8, 1999 2761
with 4-methoxyphenol (30) (100 mg, 0.80 mmol) in the pres-
ence of catalyst B (5 mol %) in CH2Cl2 (5 mL) to afford an
81:19 mixture of 47 and 49 (101 mg, 78%) as a colorless oil
(Table 1, entry 13). The two compounds were separated by
column chromatography on silica (20 × 2.5 cm) with a 9:1
hexanes-ethyl acetate mixture as an eluent. The slower
moving component was identified as 47: 1H NMR δ 3.53 (d, J
) 6.3 Hz, 2 H, 3-H), 3.75 (s, 3 H, OMe), 4.62 (br s, 1 H, OH),
6.36 (dt, J ) 16.0, 6.3 Hz, 1 H, 2-H), 6.50 (d, J ) 16.0 Hz, 1 H,
1-H), 6.66-6.77 (m, 3 H, 3′-H, 4′-H, 6′-H), 7.17-7.37 (m, 5 H,
Ph); MS (EI) m/z (%) 240 (100, M•+). The faster moving
component was identified as 49: 1H NMR δ 3.47 and 3.53 (2
× d, J ) 6.0 Hz, 2 × 2 H, 3′-H and 3′′-H), 3.79 (s, 3 H, OMe),
4.57 (s, 1 H, OH), 6.28-6.53 (m, 4 H, 1′,1′′,2′,2′′-H), 6.68 (s, 2
H, 3-H and 6-H), 7.15-7.20 (m, 10 H, 2 × Ph); MS (EI) m/z
(%) 356 (100, M•+).
of 55 and 57 (50 mg, 44%) as a colorless oil (Table 1, entry
1
16): MS (EI) m/z (%) 198 (100, M•+). 55: H NMR δ 2.26 (s, 3
H, 2′-Me), 3.49 (d, J ) 6.6 Hz, 2 H, 3-H), 5.87 and 5.92 (2 ×
m, 2 × 1 H, 3′-H and 4′-H), 6.29 (dt, J ) 15.7, 6.6 Hz; 1 H;
2-H), 6.48 (d, J ) 16.0 Hz, 1 H, 1-H), 7.17-7.38 (m, 5 H, Ph).
57: 1H NMR δ (measured in a mixture with the isomer 55)
2.23 (s, 3 H, 2′-Me), 4.67 (d, J ) 7.2 Hz, 1 H, 3- H), 5.03 (d, J
) 17.0 Hz, 1 H, 1E-H), 5.18 (d, J ) 10.1 Hz, 1 H, 1Z-H), 5.86
and 5.90 (2 × m, 2 × 1 H, 3′-H and 4′-H), 6.19 (ddd; J ) 17.0,
10.1, 7.2 Hz; 1 H; 2-H).
1-P h en yl-3-(in d ol-3′-yl)-1-bu ten e (58) a n d 4-P h en yl-4-
(in d ol-3′-yl)-2-bu ten e (60). Acetate 7 (100 mg, 0.53 mmol)
was reacted with indole (35) (70 mg, 0.60 mmol) in the
presence of catalyst B (5 mol %) in CH2Cl2 (5 mL) to produce
an inseparable 67:33 mixture of 58 and 60 (67 mg, 52%) as a
colorless oil (Table 1, entry 7): MS (EI) m/z (%) 247 (81, M•+),
117 (100). 58: 1H NMR δ (measured in a mixture with isomer
60) 1.54 (d, J ) 6.9 Hz, 3 H, 4-Me), 3.91 (p, J ) 6.9 Hz, 1 H,
3-H), 6.45 (m, 2 H, 1-H and 2-H), 6.90 (d, J ) 2.2 Hz, 1 H,
1-P h en yl-3-(1′,3′-ben zod ioxol-5′-yl)-1-p r op en e (50) a n d
5,6-Bis(1′-p h en yl-1′-p r op en -3′-yl)-1,3-b en zod ioxole (51).
Acetate 8 (100 mg, 0.57 mmol) was reacted with 1,3-benzo-
dioxole (31) (80 mg, 0.66 mmol) in the presence of catalyst B
(5 mol %) in CH2Cl2 (5 mL) to give a 79:21 mixture of 50 and
51 (90 mg, 70%) as a colorless oil (Table 1, entry 14). The two
compounds were separated by column chromatography on
silica (20 × 2.5 cm) with a 9:1 hexanes-ethyl acetate mixture
as eluent. The slower moving component was identified as 50:
1H NMR δ 3.45 (d, J ) 6.6 Hz, 2 H, 3-H), 5.91 (s, 2 H, OCH2O),
6.29 (dt, J ) 15.7, 6.6 Hz, 1 H, 2-H), 6.43 (d, J ) 15.7 Hz, 1 H,
1-H), 6.67 (dd, J ) 7.9, 1.6 Hz, 1 H, 6′-H), 6.72-6.76 (m, 2 H,
4′-H, 7′-H), 7.15-7.37 (m, 5 H, Ph); MS (EI) m/z (%) 238 (100,
1
2′-H), 6.97-7.39 (m, 9 H, arom). 60: H NMR δ (measured in
a mixture with isomer 58) 1.70 (d, J ) 6.6 Hz, 3 H, 1-Me),
4.87 (d, J ) 7.6 Hz, 1H, 4-H), 5.51 (dq, J ) 15.1, 6.3 Hz 1 H;
2-H), 5.94 (dd; J ) 15.1, 7.6 Hz; 1 H; 3-H), 6.77 (d, J ) 1.6 Hz,
1 H, 2′-H), 6.90-4.39 (arom, obscured by the signals corre-
sponding to 58).
1-P h en yl-3-(1′-m eth ylin d ol-3′-yl)-1-bu ten e (59) a n d 4-
P h en yl-4-(1′-m eth ylin d ol-3′-yl)-2-bu ten e (61). Acetate 7
(100 mg, 0.53 mmol) was reacted with 1-methylindole (36) (80
mg, 0.61 mmol) in the presence of catalyst B (5 mol %) in CH2-
Cl2 (5 mL) to afford an inseparable 85:15 mixture of 59 and
61 (118 mg, 86%) as a colorless oil (Table 1, entry 8): MS (EI)
1
M•+). The faster moving component was identified as 51: H
NMR δ 3.49 (d, J ) 5.0 Hz, 4 H, 3′-H and 3′′-H), 5.91 (s, 2 H,
OCH2O), 6.22-6.42 (m, 4 H; 1′,1′′,2′,2′′-H), 6.73 (s, 2 H, 4-H
and 7-H), 7.17-7.33 (m, 10 H, 2 × Ph); MS (EI) m/z (%) 354
(63, M•+), 250 (100).
1
m/z (%) 261 (18, M•+), 158 (100). 59: H NMR δ (measured in
a mixture with isomer 61) 1.43 (d, J ) 6.9 Hz, 3 H, 4-Me),
3.52 (s, 3 H, NMe), 3.80 (p, J ) 6.6 Hz, 1 H, 3-H), 6.35 (m, 2
H, 1-H and 2-H), 6.69 (s, 1 H, 2′-H), 6.90-7.37 (m, 9 H, arom).
1-P h en yl-3-(3′,4′-d im et h oxy-2′-m et h ylp h en yl)-1-p r o-
p en e (52) a n d 4,5-Bis(1′-p h en yl-1′-p r op en -3′-yl)-1,2-d i-
m eth oxy-3-m eth ylben zen e (53). Acetate 8 (100 mg, 0.57
mmol) was reacted with 1,2-dimethoxy-3-methylbenzene (32)
(100 mg, 0.65 mmol) in the presence of catalyst B (5 mol %) in
CH2Cl2 (5 mL) to give a 77:23 mixture of 52 and 53 (81 mg,
57%) as a colorless oil (Table 1, entry 15). The two compounds
were separated by column chromatography on silica (20 × 2.5
cm) with a 9:1 hexanes-ethyl acetate mixture as eluent. The
slower moving component was identified as 52: 1H NMR δ 2.24
(s, 3 H, 2′-Me), 3.46 (d, J ) 4.7 Hz, 2 H, 3-H), 3.78 (s, 3 H,
3′-OMe), 3.83 (s, 3 H, 4′-OMe), 6.23-6.38 (m, 2 H, 1-H and
2-H), 6.71 (d, J ) 8.2, 5′-H), 6.89 (d, J ) 8.4 Hz, 6′-H), 7.14-
7.35 (m, 5 H, Ph); NOESY NMR δ 2.24 (2′-Me) T 3.46 (3-H),
2.24 (2′-Me) T 6.32 (1- and 2-H), 2.24 (2′-Me) T 3.78 (3′- OMe),
3.46 (3-H) T 6.89 (6′-H), 3.83 (4′-OMe) T 6.71 (5′-H); MS (EI)
m/z (%) 268 (100, M•+). The faster moving component was
1
61: H NMR δ (measured in a mixture with isomer 59) 1.60
(d, J ) 6.6 Hz, 3 H, 1-Me), 3.51 (s, 3 H, NMe), 4.76 (d, J ) 7.2
Hz, 1 H, 4-H), 5.51 (dq, J ) 15.1, 6.3 Hz, 1 H, 2-H), 5.94 (dd,
J ) 15.1, 7.5 Hz, 1 H, 3-H), 6.63 (s, 1 H, 2′-H).
1-Meth yl-3-(4′-m eth oxyp h en yl)cycloh exen e (62). Ac-
etate 15 (100 mg, 0.65 mmol) was reacted with anisole 26 (100
mg, 0.93 mmol) at -10 °C in the presence of catalyst B (5 mol
%) in CH2Cl2 (5 mL) to give 62 (65 mg, 50%) as a colorless oil
(Table 2, entry 2): 1H NMR δ 1.36-2.02 (m, 6 H, 3 × CH2),
1.73 (s, 3 H, 1-Me), 3.31 (m, 1 H, 3-H), 3.77 (s, 3 H, OMe),
5.41 (br s, 1 H, 2-H), 6.82 (d, J ) 8.5 Hz, 2 H 3′-H, 5′-H), 7.11
(d, J ) 8.5 Hz, 2 H, 2′-H, 6′-H); 13C NMR δ 22.0, 30.4, 32.9
(4,5,6-CH2), 24.4 (1-Me), 41.7 (3-CH), 55.7 (OMe), 114.0 (3′,5′-
CH), 125.2 (2-CH), 129.0 (2′,6′-H), 135.5 and 139.8 (1-C and
1′-C), 158.2 (4′-C); MS (EI) m/z (%) 202 (98, M•+), 187 (100).
1-Meth yl-3-(4′-h yd r oxyp h en yl)cycloh ex-1-en e (63), 1-
Met h yl-3-(2′-h yd r oxyp h en yl)cycloh ex-1-en e (66), a n d
3,4,5,6-Tet r a h yd r o-2-m et h yl-2,6-m et h a n o-2H -1-b en zo-
cin (73).37l Acetate 15 (100 mg, 0.65 mmol) was reacted with
phenol (27) (330 mg, 3.51 mmol) in the presence of catalyst B
(5 mol %) in CH2Cl2 (5 mL). Column chromatography of the
crude product on silica gel (15 × 2 cm) with a 9:1 hexanes-
ethyl acetate mixture as eluent afforded (in the order of
elution) 63 (46 mg, 38%) and 73 (26 mg, 21%) as colorless oils
(Table 2, entry 3). The same reaction with catalyst C (5 mol
%) afforded 73 (25 mg, 20%) and a 1:4 mixture of 63 and 66
(29 mg, 24%). (Table 2, entry 4). The latter mixture was
separated by preparative HPLC on Partisil 10 column with a
95:5 mixture hexanes-ethyl acetate (Table 1, entry 4). 63: 1H
NMR δ 1.25-1.95 (m, 6 H, 3 × CH2), 1.61 (s, 3 H, 1-Me), 3.18
(m, 1 H, 3-H), 5.28 (br s, 2 H, 2-H and OH), 6.65 (d, J ) 8.5
Hz, 2H, 3′-H, 5′-H), 6.94 (d, J ) 8.5 Hz, 2 H, 2′-H, 6′-H); 13C
NMR δ 21.9, 30.3, 32.9 (4,5,6-CH2), 24.4 (1-Me), 41.7 (3-CH),
115.4 (3′,5′-CH), 125.1 (2-CH), 129.2 (2′,6′-CH), 135.6 and 140.0
(1-C and 1′-C), 153.9 (4′-C); MS (EI) m/z (%) 188 (96, M•+), 120
1
identified as 53: H NMR δ 2.27 (s, 3 H, 3-Me), 3.54 (d, J )
4.7 Hz, 4 H, 3′-H and 3′′-H), 3.78 (s, 3 H, OMe), 3.85 (s, 3 H,
OMe), 6.17-6.37 (m; 4 H; 1′-H, 1′′-H, 2′-H, 2′′-H), 6.68 (s, 1 H,
6-H), 7.14-7.33 (m, 10 H, 2 × Ph); MS (EI) m/z (%) 384 (100,
M•+).
1-P h en yl-3-(2′-m et h ylfu r a n -5′-yl)-1-b u t en e (54) a n d
4-P h en yl-4-(2′-m eth ylfu r a n -5′-yl)-2-bu ten e (56). Acetate 7
(100 mg, 0.53 mmol) was reacted with 2-methylfuran (33) (82
mg, 1.00 mmol) in the presence of catalyst B (5 mol %) in CH2-
Cl2 (5 mL) to furnish an inseparable 84:16 mixture of 54 and
56 (100 mg, 90%) as a colorless oil (Table 1, entry 6): MS (EI)
m/z (%) 212 (100, M•+). 54: 1H NMR δ (measured in a mixture
with the 56)1.31 (d, J ) 6.9 Hz, 3 H, 4-Me), 2.14 (s, 3 H, 2′-
Me), 3.51 (p, J ) 6.9 Hz, 1 H, 3-H), 5.76 and 5.80 (2 × m, 2 ×
1 H, 3′-H and 4′-H), 6.16 (dd; J ) 15.7, 7.2 Hz, 1 H, 2-H), 6.32
(d, J ) 16.0 Hz, 1 H, 1-H), 7.01-7.48 (m, 5 H, Ph). 56: 1H
NMR δ (measured in a mixture with the 54) 1.59 (d, J ) 6.6
Hz, 3 H, 1-Me), 2.11 (s, 3 H, 2′-Me), 4.51 (d, J ) 7.6 Hz, 1 H,
4-H), 5.43 (m, 1 H, 2-H), 5.69 (m, 1 H, 3-H).
1-P h en yl-3-(2′-m eth ylfu r a n -5′-yl)-1-p r op en e (55)37g a n d
3-P h en yl-3-(2′-m eth yl-fu r a n -5′-yl)-1-p r op en e (57).37g Ace-
tate 8 (100 mg, 0.57 mmol) was reacted with 2-methylfuran
(33) (60 mg, 0.73 mmol) in the presence of catalyst B (5 mol
%) in CH2Cl2 (5 mL) to produce an inseparable 75:25 mixture
(100). 66: H NMR δ 1.52-2.10 (m, 6 H, 3 × CH2), 1.70 (s, 3
1
H, 1-Me), 3.48 (m, 1 H, 3-H), 5.51 (s, 1 H, OH), 5.58 (s, 1H,
2-H), 6.82 (m, 2H, 3′-H, 5′-H), 7.10 (m, 2 H, 2′-H, 6′-H). 73: 1H
NMR δ 1.35 (s, 3 H, 2-Me), 1.43-1.81 (m, 8 H, 4 × CH2), 3.04
(m, 1 H, 6-H), 6.78 (m, 2 H, 8-H and 10-H), 6.98 (d, J ) 7.6

2762 J . Org. Chem., Vol. 64, No. 8, 1999
Malkov et al.
Hz, 1 H, 7-H), 7.09 (t, J ) 6.9 Hz, 1 H, 9-H);13C NMR δ 18.7,
33.0, 36.3, and 39.8 (3,4,5,11-CH2), 29.8 (2-Me), 33.4 (6-CH),
75.1 (2-C), 115.4 (10-CH), 119.5 (8-CH), 126.4 (6a-C), 127.7
and 128.5 (7- and 9-CH), 157.9 (10a-C); MS (EI) m/z (%) 188
(77, M•+), 120 (100).
6.87 (m, 2 H, 4′-H and 6′-H); MS (EI) m/z (%) 188 (100, M•+).
The faster moving component was identified as 2,6-bis-
(cyclohex-2′-en-1′-yl)-4-methylphenol: 1H NMR δ 1.55-2.12
(m, 12 H, 6 × CH2), 2.24 (s, 3 H, 4-Me), 3.58 (m, 2 H, 1′-H,
1′′-H), 5.59 (s, 1 H, OH), 5.79 (d, J ) 10.1, 2 H, 2′-H, 2′′-H),
6.00 (ddd, J ) 10.1, 6.0, 3.5 Hz, 1 H, 3′-H, 3′′-H), 6.80 (s, 2 H,
3-H and 5-H); MS (EI) m/z (%) 268 (100, M•+).
3,4,5,6-Tetr ah ydr o-2,8-dim eth yl-2,6-m eth an o-2H-1-ben -
zocin (74). Acetate 15 (100 mg, 0.65 mmol) was reacted with
p-cresol (29) (710 mg, 6.57 mmol) in the presence of catalyst
B (5 mol %) in CH2Cl2 (5 mL) to afford 74 (101 mg, 77%) as a
colorless oil (Table 2, entry 5): 1H HMR δ 1.38 (s, 3 H, 2-Me),
1.48-1.97 (m, 8H, 4 × CH2), 2.29 (s, 3 H, 8-Me) 3.02 (p, J )
3.1 Hz, 1 H, 6-H), 6.72 (d, J ) 8.2 Hz, 1 H, 10-H), 6.83 (d, J )
1.9 Hz, 1 H, 7-H), 6.94 (dd, J ) 8.2 Hz, J ) 1.9 Hz, 1 H, 9-H);
13C NMR δ 18.8, 33.1, 36.5, 40.0 (3,4,5,11-CH2), 20.9 (8-Me),
29.9 (2-Me), 33.5 (6-CH), 74.9 (2-C), 115.2 (10-CH), 126.1 and
128.4 (6a- and 8-C), 128.5 and 129.0 (7- and 9-CH), 154.9 (10a-
C); IR ν 3020, 2980, 2925, 2870, 2850, 1620, 1590, 1490, 1450
cm-1; MS (EI) m/z (%) 202 (100, M•+).
3,4,5,6-Tet r a h yd r o-2,4,4,8-t et r a m et h yl-2,6-m et h a n o-
2H-1-ben zocin (76). Acetate 16 (294 mg, 1.62 mmol) was
reacted with p-cresol (29) (2.06 g, 19.07 mmol) in the presence
of catalyst B (5 mol %) in CH2Cl2 (5 mL) to furnish 76 (298
mg, 80%) as a colorless oil (Table 2, entry 9): 1H NMR δ 0.58
(s, 3 H, 4-Mea), 0.90 (s, 3 H, 4-Meb), 1.4 (s, 3 H, 2-Me), 1.45-
1,89 (m, 6 H, 3 × CH2), 2.27 (s, 3 H, 8-Me), 3.0 (p, J ) 3.5 Hz,
1 H, 4-H), 6.63 (d, J ) 8.2 Hz, 1 H, 10-H), 6.87 (d, J ) 2.2 Hz,
1 H, 7-H), 6.94 (dd, J ) 8.2, 2.2 Hz, 1 H, 9-H); 13C NMR δ 20.9
(8-Me), 29.7, 30.6 and 33.1 (2,4,4-Me), 30.0 (4-C), 36.5, 45.7
and 52.1 (3,5,11-CH2), 37.2 (6-CH), 75.3 (2-C), 115.4 (10-CH),
127.5 and 128.5 (6a- and 8-C), 128.8 and 129.0 (7- and 9-CH),
153.9 (10a); IR ν 3060, 3010, 2980-2860, 2840, 1620, 1590,
1500, 1460 cm-1; MS (EI) m/z (%) 230 (100, M•+).
1,5,5-Tr im eth yl-3-(4′-h ydr oxyph en yl)cycloh ex-1-en e (64)
a n d 3,4,5,6-Tetr a h yd r o-2,4,4-tr im eth yl-2,6-m eth a n o-2H-
1-ben zocin (75). Acetate 16 (100 mg, 0.55 mmol) was reacted
with phenol (27) (150 mg, 1.60 mmol) in the presence of
catalyst B (5 mol %) in CH2Cl2 (5 mL). Column chromatogra-
phy of the crude product on silica gel (15 × 2 cm) with a 9:1
hexanes-ethyl acetate mixture as eluent afforded (in the order
of elution) 64 (10 mg, 8%) and 75 (17 mg, 14%) as colorless
1
oils (Table 2, entry 8). 64: H NMR δ 0.96 (s, 6 H, 2 × 5-Me),
1.50-1.90 (m, 4 H, 4-H and 6-H), 1.71 (s, 3 H, 1-Me), 3.30 (m,
1 H, 3-H), 4.91 (br s, 1 H, OH), 5.36 (br s, 1 H, 2-H), 6.76 (d,
J ) 8.5 Hz, 2 H, 3′-H,5′-H), 7.06 (d, J ) 8.5 Hz, 2 H, 2′-H,
6′-H); 13C NMR δ 23.0 and 24.2 (2 × 5-Me), 29.4 (5-C), 30.8
(1-Me), 39.0 (3-CH), 43.0 and 45.3 (4- and 6-CH2), 114.1 (3′,5′-
CH), 122.6 (2-CH), 127.7 (2′,6′-CH), 133.7 and 138.7 (1-C and
1′-C), 152.6 (4′-C); MS (EI) m/z (%) 216 (62, M•+), 98 (100). 75:
1H NMR δ 0.54 (s, 3 H, 4-Mea), 0.89 (s, 3 H, 4-Meb), 1.40 (s, 3
H, 2-Me), 1.54-1.92 (m, 6 H, 3 × CH2), 3.03 (p, J ) 3.3 Hz, 1
H, 6-H), 6.70 (d, J ) 8.2 Hz, 1 H, 10-H), 6.77 (t, J ) 7.4 Hz, 1
H, 8-H), 7.07 (m, 2 H, 7-H and 9-H); 13C NMR δ 29.6, 30.6,
and 33.1 (2, 4,4-Me), 29.9 (4-C), 37.2 (6-CH), 36.3, 45.7, and
52.0 (3,5,11-CH2), 75.5 (2-C), 115.7 (10-CH), 119.5 (8-CH),
127.9 and 128.5 (7- and 9-CH), 128.1 (6a), 156.1 (10a); MS (EI)
m/z (%) 216 (90, M•+) 145 (100).
3-(4′-Meth oxyp h en yl)cycloh ex-1-en e (65)37h a n d 3-(2′-
Meth oxyp h en yl)cycloh ex-1-en e (70).37i Acetate 17 (100 mg,
0.71 mmol) was reacted with anisole (26) (150 mg, 1.39 mmol)
in the presence of catalyst B (5 mol %) in CH2Cl2 (5 mL) to
produce a 57:43 mixture of 65 and 70 (75 mg, 56%) as a
colorless oil (Table 2, entry 11). The two compounds were
separated by column chromatography on silica gel (20 × 2.5
cm) with a 95:5 hexanes-ethyl acetate mixture (95:5) as
eluent. The slower moving component was identified as 65:
1H NMR δ 1.45-2.12 (m, 6 H, 3 × CH2), 3.34 (m, 1 H, 3-H),
3.78 (s, 3 H, OMe), 5.69 (dd, J ) 10.1, 1.9 Hz, 1 H, 2-H), 5.86
(ddd, J 10.1, 6.0, 3.5 Hz, 1 H, 1-H), 6.84 (d, J ) 8.5 Hz, 2 H,
3′-H, 5′-H), 7.13 (d, J ) 8.5 Hz, 2 H, 2′-H, 6′-H); MS (EI) m/z
(%) 188 (M+, 100). The faster moving component was identified
3-(4′-Meth oxyp h en yl)cyclop en t-1-en e (77).37h Acetate 19
(100 mg, 0.79 mmol) was reacted with anisole (26) (150 mg,
1.39 mmol) in the presence of catalyst B (5 mol %) in CH2Cl2
(5 mL) to give an 80:20 mixture of 77 and bis-allylated products
(64 mg, 50%) as a colorless oil (Table 2, entry 16). The GS-MS
analysis of the crude product mixture showed the presence of
two compounds (11% and 9%) with the molecular ion 240 cor-
responding to the isomeric bis-allylated products. Pure 77 was
obtained from that mixture by column chromatography on
silica gel (20 × 2.5 cm) with a 9:1 hexanes-ethyl acetate mix-
ture as an eluent: 1H NMR δ 1.58-1.68 and 2.11-2.45 (2 ×
m, 4 H, 2 × CH2), 3.73 (s, 3 H, OMe), 3.79 (m, 1 H, 3-H), 5.70
(ddd, J ) 5.7, 3.8, 1.9 Hz, 1 H, 2-H), 5.85 (ddd, J ) 5.7, 4.4,
2.2 Hz, 1 H, 1-H), 6.78 (d, J ) 8.5 Hz, 2 H, 3′-H, 5′-H), 7.05 (d,
J ) 8.8 Hz, 2 H, 2′-H, 6′-H); MS (EI) m/z (%) 174 (100, M•+).
3-(2′-Hyd r oxyp h en yl)cyclop en t-1-en e (78).37i Acetate 19
(100 mg, 0.79 mmol) was reacted with phenol (27) (200 mg,
2.13 mmol) in the presence of catalyst B (5 mol %) in CH2Cl2
(5 mL) to give an 87:13 mixture of 78 and a bis-allylated
products (48 mg, 41%) as a colorless oil (Table 2, entry 17).
The GS-MS analysis of the crude product mixture showed the
presence of two compounds (8% and 5%) with the molecular
ion 226 corresponding to the isomeric bis-allylated products.
Pure 78 was obtained from that mixture by column chroma-
tography on silica gel (20 × 2.5 cm) with a 9:1 hexanes-ethyl
acetate mixture as an eluent: 1H NMR δ 1.53-1.84 and 2.36-
2.57 (2 × m, 4 H, 4-H, 5-H), 4.05 (m, 1 H, 3-H), 5.28 (br s, 1 H,
OH), 5.89 (m, 1 H, 2-H), 6.07 (m, 1 H, 1-H), 6.71-7.26 (m, 4H,
3′-H, 6′-H); MS (EI) m/z (%) 160 (100, M•+).
1
as 70: H NMR δ 1.47-2.07 (m, 6 H; 3 × CH2), 3.82 (s, 3 H,
OMe), 3.85 (m, 1 H, 3-H), 5.66 (dd, J ) 10.1, 2.5 Hz, 1 H, 2-H),
5.90 (ddd, J ) 10.1, 6.0, 3.8 Hz, 1 H, 1-H), 6.89 (m, 2 H, 3′-H,
5′-H), 7.18 (m, 2 H, 4′-H, 6′-H); MS (EI) m/z (%) 188 (100, M•+).
3-(2′-Hyd r oxyp h en yl)cycloh exen e (71).37j Acetate 17
(100 mg, 0.71 mmol) was reacted with phenol (27) (200 mg,
2.13 mmol) in the presence of catalyst B (5 mol %) in CH2Cl2
(5 mL) to afford a 90:10 mixture of 71 and a bis-allylated
product (93 mg, 79%) as a colorless oil (Table 2, entry 13). GS-
MS showed the molecular ions for the two products to be 174
and 254. The same reaction with catalyst C (5 mol %) gave
rise to a 95:5 mixture of 71 and a bis-allylated product (101
mg, 83%) (Table 2, entry 14). Column chromatography of the
former mixture on silica gel (20 × 2.5 cm) with a 9:1 hexanes-
ethyl acetate mixture as eluent furnished 71 (90 mg): 1H NMR
δ 1.48-2.17 (m, 6 H, 3 × CH2), 3.58 (m, 1 H, 3-H), 5.46 (s, 1
H, OH), 5.80 (dm, J ) 10.1 Hz, 1 H, 2-H), 6.04 (ddd, J ) 10.1,
6.0, 3.2 Hz, 1 H, 1-H), 6.71-6.96 (m, 3 H, 3′-H, 5′-H, 6′-H),
7.10 (m, 1 H, 4′-H); MS (EI) m/z (%) 174 (100, M•+).
3-(2′-Hyd r oxy-5′-m eth ylp h en yl)cycloh ex-1-en e (72)37k
a n d 2,6-Bis(cycloh ex-2′-en -1′-yl)-4-m eth ylp h en ol. Acetate
17 (130 mg; 0.92 mmol) was reacted with p-cresole (29) (385
mg, 3.56 mmol) in the presence of catalyst C (5 mol %) in CH2-
Cl2 (5 mL) to produce an 84:16 mixture of 72 and 2,6-bis(2′-
cyclohexenyl)-4-methylphenol (150 mg, 91%) as a colorless oil
(Table 2, entry 15). The two compounds were separated by
column chromatography on silica (20 × 2.5 cm) with a 9:1
hexanes-ethyl acetate mixture as eluent. The slower moving
3-(1′,3′-Ben zod ioxol-5′-yl)-cyclop en t-1-en e (79). Acetate
19 (100 mg, 0.79 mmol) was reacted with 1,3-benzodioxole (31)
(150 mg, 1.23 mmol) in the presence of catalyst B (5 mol %) in
CH2Cl2 (5 mL) to furnish 79 (70 mg, 47%) as a colorless oil
(Table 2, entry 18): 1H NMR δ 1.51-1.63 and 2.20-2.40 (2 ×
m, 4 H, 4-H, 5-H), 3.72 (m, 1 H, 3-H), 5.64 (m, 2 H, 1-H, 2-H),
5.81 (s, 2 H, OCH2O), 6.55 (dd, J ) 7.9, 1.6 Hz, 1 H, 6′-H),
6.58 (d, J ) 1.6 Hz, 1 H, 4′-H), 6.63 (d, J ) 7.9 Hz, 1 H, 7′-H);
MS (EI) m/z (%) 188 (100, M•+).
1
component was identified as 72: H NMR δ 1.58-2.14 (m, 6
H; 3 × CH2), 2.24 (s, 3 H, 5′-Me), 3.54 (m, 1 H, 3-H), 5.35 (s,
1 H, OH), 5.79 (dd, J ) 10.1, 2.1 Hz, 1 H, 2-H), 6.01 (ddd, J )
10.1, 6.0, 3.5 Hz, 1 H, 1-H), 6.67 (d, J ) 7.9 Hz, 1 H, 3′-H),
3-(3′,4′-Dim et h oxy-2′-m et h ylp h en yl)-cyclop en t -1-en e
(80). Acetate 19 (100 mg, 0.79 mmol) was reacted with 1,2-
dimethoxy-3-methylbenzene (32) (160 mg, 1.05 mmol) in the

Molybdenum(II)-Catalyzed Allylation
J . Org. Chem., Vol. 64, No. 8, 1999 2763
presence of catalyst B (5 mol %) in CH2Cl2 (5 mL) to furnish
80 (128 mg, 74%) as a colorless oil (Table 2, entry 19): 1H NMR
δ 1.50-1.65 and 2.35-2.46 (2 × m, 4 H, 4-H, 5-H), 2.27 (s, 3
H, 2′-Me), 3.77 (s, 3 H, OMe), 3.80 (s, 3 H, OMe), 4.01 (m, 1 H,
3-H), 5.73 (ddd, J ) 5.7, 4.1, 1.9 Hz,1 H, 2-H), 5.92 (ddd, J )
5.7, 4.3, 2.0 Hz, 1 H, 1-H), 6.68 (d, J ) 8.5 Hz, 1 H, 5′-H), 6.81
(d, J ) 8.5 Hz, 1 H, 6′-H); MS (EI) m/z (%) 218 (30, M•+), 152
(100).
H, 1′-H), 5.00 (s, 2 H, OCH2), 5.47 (m, 1 H, 2′-H), 5.94 (d, J )
3.2 Hz, 1 H, 4-H), 6.29 (d, J ) 3.2 Hz, 1 H, 3-H); 13C NMR δ
21.2 (CH3CO), 24.3 (3′-CH3), 21.3, 28.2 and 30.3 (4′,5′,6′-CH2),
35.7 (1′-CH), 58.8 (OCH2), 105.8 and 111.7 (3,4-CH), 121.3 (2′-
CH), 136.5 (C), 148.0 (C), 161.0 (C), 171.1 (CO); MS (EI) m/z
(%) 234 (12, M•+), 79 (100).
1-Meth yl-3-(1′-m eth ylin dol-3′-yl)cycloh ex-1-en e (88). Ac-
etate 15 (100 mg, 0.65 mmol) was reacted with 1-methylindole
(36) (100 mg, 0.76 mmol) in the presence of catalyst B (5 mol
%) in CH2Cl2 (5 mL) to furnish 88 (125 mg, 85%) as a colorless
oil (Table 2, entry 7): 1H NMR δ 1.63-2.01 (m, 6 H, 3 × CH2),
1.73 (s, 3 H, 1-Me), 3.64 (s, 3 H, NMe), 3.67 (m, 1 H, 3-H),
5.57 (m, 1 H, 2-H), 6.74 (s, 1 H, 2′-H), 7.06 (t, J ) 7.9 Hz, 1 H,
5′-H), 7.22 (m, 2 H, 6′-H and 7′-H), 7.61 (d, J ) 7.9 Hz, 1 H,
4′-H); MS (EI) m/z (%) 225 (100, M•+).
2-Met h yl-4-(4′-m et h oxyp h en yl)-2-b u t en e (81).37m Ac-
etate 20 (100 mg, 0.70 mmol) was reacted with anisole (26)
(100 mg, 0.93 mmol) in the presence of catalyst B (5 mol %) in
CH2Cl2 (5 mL) to furnish 81 (32 mg, 24%) as a colorless oil
(Table 2, entry 20): 1H NMR δ 1.27 (d, J ) 6.9 Hz, 3 H, 5-CH3),
1.67 and 1.69 (2 × d, J ) 1.5 and 1.2 Hz, 2 × 3 H, 1- and 2-
CH3), 3.61 (m, 1 H, 4-H), 3.78 (s, 3 H, OMe), 5.24 (dm, J ) 9.1
Hz, 1 H, 3-H), 6.83 (d, J ) 8.5 Hz, 2 H, 3′-H and 5′-H), 7.14 (d,
J ) 8.5 Hz, 2 H, 2′-H and 6′-H); MS (EI) m/z (%) 190 (28, M•+),
175 (100).
1,5,5-Tr im e t h yl-3-(1′-m e t h ylin d ol-3′-yl)cycloh e x-1-
en e (89). Acetate 16 (141 mg, 0.78 mmol) was reacted with
1-methylindole (36) (514 mg, 3.92 mmol) in the presence of
catalyst B (5 mol %) in CH2Cl2 (5 mL) to furnish 89 (143 mg,
70%) as a colorless oil (Table 2, entry 10): 1H HMR δ 0.95 (s,
3 H, 5-Mea), 1.02 (s, 3 H, 5-Meb), 1.45-1.95 (m, 4 H, 4-H and
6-H), 1.70 (s, 3 H, 3-Me), 3.65 (s, 3 H, NMe), 5.50 (br s, 1 H,
2-H), 6.70 (s, 1 H, 2′-H), 7.02 (m, 1 H, 5′-H), 7.19 (m, 2 H, 6′-
and 7′-H), 7.68 (d, J ) 9.0 Hz, 1 H, 4′-H); 13C NMR δ 24.4 and
25.8 (2 × 5-Me), 30.8 (5-C), 32.0 (1-Me), 32.4 (NMe), 33.0 (3-
CH), 44.5 and 44.7 (4- and 6-CH2), 109.7 (CH), 118.9 (CH),
120.0 (CH), 120.5 (C), 121.9 (CH), 124.4 (CH), 125.6 (CH),
127.6 (C), 133.3 (C), 137.8 (C); MS (EI) m/z (%) 262 (100, M•+).
(E)-3-(2′-Hyd r oxyp h en yl)-5-ca r bom eth oxy-1-cycloh ex-
en e (90) a n d (E)-3-(4′-Hyd r oxyp h en yl)-5-ca r bom eth oxy-
1-cycloh exen e (91). Acetate 23 (100 mg, 0.51 mmol) was
reacted with phenol (27) (100 mg, 1.06 mmol) in the presence
of catalyst B (5 mol %) in CH2Cl2 (5 mL) to give a 90:10 mixture
of o- and p-isomers 90 and 91 (69 mg, 59%) as a white solid
(Table 2, entry 26): MS (EI) m/z (%) 232 (77, M•+), 172 (100).
Compounds 90 and 91 were separated by preparative HPLC
with a 98:2 hexanes-ethyl acetate mixture as an eluent. 90:
1H NMR δ 2.08 (m, 2 H, 4-H), 2.38 (m, 2 H, 6-H), 2.61 (m, 1 H,
5-H), 3.65 (s, 3 H, OMe), 3.88 (m, 1 H, 3-H), 5.78 (m, 1 H, 1-H),
5.98 (m, 1 H, 2-H), 6.03 (s, 1 H, OH), 6.76-6.88 (m, 2 H, 3′-
and 5′-H), 7.08 (m, 2 H, 4′- and 6′-H). 91: 1H NMR δ 1.92 (dt,
J ) 12.9, 3.5 Hz, 1 H, 4-Ha), 2.12 (ddd, J ) 12.9, 10.7, 6.0 Hz,
1 H, 4-Hb), 2.34 (m, 2 H, 6-H), 2.59 (m, 1 H, 5-H), 3.50 (m, 1
H, 3-H), 3.65 (s, 3 H, OMe), 4.74 (s, 1 H, OH), 5.74 (m, 1 H,
1-H), 5.93 (m, 1 H, 2-H), 6.77 (d, J ) 8.5 Hz, 2 H, 3′-H and
5′-H), 7.08 (d, J ) 8.5 Hz, 2 H, 4′-H and 6′-H).
1-(2′-H yd r oxyp h e n yl)-3a ,4,5,6,7,7a -h e xa h yd r o-(1r,-
3a R,4R,7R,7a R)-4,7-m eth a n o-1H-in d en e (92). Acetate 24
(100 mg, 0.52 mmol) was reacted with phenol (27) (490 mg,
5.21 mmol) in the presence of catalyst B (5 mol %) in CH2Cl2
(5 mL) to afford 92 (59 mg, 51%) as a colorless oil (Table 2,
entry 29): 1H NMR δ 1.25-1.46 (m, 6 H, 3 × CH2), 2.37 (m, 3
H, 4-H, 7-H, 7a-H), 3.22 (m, 1 H, 3a-H), 3.88 (br s, 1 H, 1-H),
5.37 (s, 1 H, OH), 5.86 (m, 2 H, 2-H, 3-H), 6.80 (m, 2 H, 3′-H,
5′-H), 7.05 (m, 2 H, 2′-H, 6′-H); 13C NMR δ 23.3 and 25.6 (5,6-
CH2); 39.6, 41.6, 47.4 (4,7,7a-CH), 41.6 (8-CH2), 52.9 and 53.6
(1,3a-CH); 116.5, 121.0, 127.8, and 129.4 (3′-6′-CH), 132.3 (1′-
C), 133.8 and 136.6 (2,3-CH), 154.7 (2′-CH); MS (EI) m/z (%)
226 (22, M•+), 159 (100).
2-Meth yl-4-(4′-m eth oxyph en yl)-2-bu ten e (82).37n-s Meth -
od A. Acetate 21 (100 mg, 0.78 mmol) was reacted with anisole
(26) (100 mg, 0.93 mmol) in the presence of the catalyst B (5
mol %) in CH2Cl2 (5 mL) to furnish a 73:27 mixture of 82 and
the corresponding ortho-isomer (57 mg, 42%) as a colorless oil
(Table 2, entry 22). Pure 82 was obtained from that mixture
by column chromatography on silica gel (20 × 2.5 cm) with a
95:5 hexanes-ethyl acetate mixture as an eluent: 1H NMR δ
1.71 (s, 3 H, Me), 1.73 (s, 3 H, Me), 3.27 (d, J ) 7.2 Hz, 2 H,
4-H), 3.77 (s, 3 H, OMe), 5.24 (br t, J ) 7.2 Hz, 1 H, 3-H), 6.82
(d, J ) 8.8 Hz, 2 H, 3′-H and 5′-H), 7.18 (d, J ) 8.5 Hz, 2 H,
2′-H and 6′-H); MS (EI) m/z (%) 176 (36, M•+), 121 (100).
Meth od B. The reaction of 22 with anisole (26) was carried
out as described in method A to afford 82 (65 mg, 47%; Table
2, entry 24). The GC-MS analysis of the product showed the
presence of the ortho isomer (less than 5%).
3,4-Dih yd r o-2,2,4-tr im eth yl-2H-ben zop yr a n (85).37t Ac-
etate 20 (80 mg, 0.56 mmol) was reacted with phenol (27) (260
mg, 2.77 mmol) in the presence of catalyst B (5 mol %) in CH2-
Cl2 (5 mL) to give an 95:5 mixture of 85 and bis-allylated
products (19 mg, 19%) as a colorless oil (Table 2, entry 21).
The GS-MS analysis of the crude product mixture showed the
presence of two compounds (3% and 2%) with the molecular
ions 258 corresponding to the isomeric bis-allylated products.
Pure 85 was obtained from that mixture by column chroma-
tography on silica gel (20 × 2.5 cm) with a 9:1 hexanes-ethyl
acetate mixture as an eluent: 1H NMR δ 1.25 (s, 3 H, Me),
1.41 (s, 3 H, Me), 1.33 (d, J ) 6.6 Hz, 3 H, 4-Me), 1.70 (m, 2 H,
CH2), 2.95 (m, 1 H, 4-H), 6.76 (d, J ) 8.2 Hz, 1 H, 8-H), 6.85
(t, J ) 7.5 Hz, 1 H, 6-H), 7.08 (dd; J ) 8.2, 7.3 Hz; 1 H, 7-H),
7.23 (d, J ) 7.5 Hz, 1 H, 5-H); 13C NMR δ 20.7 and 25.0 (2 ×
2-Me), 26.7 (4-CH), 30.5 (4-Me), 43.1 (3-CH2), 74.7 (2-C), 117.6
and 120.2 (6- and 8-CH), 127.5 and 127.7 (5- and 7-CH), 126.7
(4a-C), 153.9 (8a-C); MS (EI) m/z (%) 176 (46, M•+), 121 (100).
3,4-Dih yd r o-2,2-d im eth yl-2H-ben zop yr a n (86).37h Meth -
od A. Acetate 21 (100 mg, 0.78 mmol) was reacted with phenol
(27) (150 mg, 1.60 mmol) in the presence of catalyst B (5 mol
%) in CH2Cl2 (5 mL) to afford a 90:10 mixture of 86 and a bis-
allylated product (32 mg, 27%) as a colorless oil (Table 2, entry
23). Pure 86 was obtained from that mixture by column chrom-
atography on silica gel (20 × 2.5 cm) with a 9:1 hexanes-ethyl
acetate mixture as an eluent: 1H NMR δ 1.33 (s, 6 H, 2 ×
2-CH3), 1.80 (m, 2 H, 3-H), 2.77 (t, J ) 6.9 Hz, 2 H, 4-H), 6.71-
7.11 (m, 4 H, arom); 13C NMR δ 22.9 (3-CH2), 27.3 (2 × 2-Me),
33.2 (4-CH2), 74.5 (2-C), 117.7 and 120.0 (6- and 8-CH), 121.3
(4a-C), 127.7 and 129.8 (5- and 7-CH), 154.4 (8a-C).
1-(4′-Me t h oxyp h e n yl)-3a ,4,5,6,7,7a -h e xa h yd r o-(1R,-
3a R,4R,7R,7a R)-4,7-m eth a n o-1H-in d en e (93). Acetate 24 (70
mg, 0.36 mmol) was reacted with anisole (26) (560 mg, 5.19
mmol) in the presence of catalyst B (5 mol %) in CH2Cl2 (5
mL) to afford 93 (66 mg, 75%) as a colorless oil (Table 2, entry
28). The GC-MS analysis of the product showed the presence
of bis-allylated compound (∼10%): 1H NMR (taken in a
mixture with bis-allylation product) δ 1.25 (m, 6 H, 3 × CH2),
2.30 (m, 3 H, 4-H, 7-H, 7a-H), 3.15 (m, 1 H, 3a-H), 3.54 (m, 1
H, 1-H), 3.76 (s, 3 H, OMe), 5.70 (m, 2 H, 2-H, 3-H), 6.80 (d, J
) 8.5 Hz, 2 H, 3′-H, 5′-H), 7.04 (d, J ) 8.5 Hz, 2 H, 2′-H, 6′-
H); MS (EI) m/z (%) 240 (27, M•+), 173 (100).
Meth od B. The reaction of 22 with phenol (27) was carried
out as described in method A to afford an 80:20 mixture of 86
and a bis-allylated product (55 mg, 48%) as a colorless oil
(Table 2, entry 25), identical with the product obtained from
21 and 27 (see above).
5-(3′-Meth ylcycloh ex-2′-en -1′-yl)fu r fu r yl Aceta te (87).
Acetate 15 (120 mg, 0.78 mmol) was reacted with furfuryl
acetate (34) (140 mg, 1.0 mmol) in the presence of catalyst B
(5 mol %) in CH2Cl2 (5 mL) to yield 87 (120 mg, 65%) as a
colorless oil (Table 2, entry 6): 1H NMR δ 1.56-1.94 (m, 6 H,
3 × CH2), 1.70 (s, 3 H, 3′-Me), 2.07 (s, 3 H, MeCO), 3.42 (m, 1
(R)-(+)-1-P h en yl-3-p h en oxy-1-bu t en e (102) was pre-
pared by following the literature procedure11 from carbonate
(R)-(+)-101 (360 mg, 1.64 mmol) and phenol (160 mg, 1.7
mmol) in 75% yield (276 mg, 1.23 mmol): [R]D +81.7 (c 2.1,

2764 J . Org. Chem., Vol. 64, No. 8, 1999
Malkov et al.
1
CHCl3); H NMR δ 1.52 (d, J ) 6.3 Hz, 3 H, 4-Me), 4.97 (p, J
Meth od B. Analogously, a solution of (R)-(+)-104 (30 mg,
0.11 mmol) in CH2Cl2 (5 mL) was treated with Yb(OTf)3 for
12 h at room temperature to afford 105 (17 mg, 57%) with no
optical rotation detected.
) 6.3 Hz, 1 H, 3-H), 6.28 (dd, J ) 16.0, 6.0 Hz, 1 H, 2-H), 6.60
(d, J ) 16.3 Hz, 1 H, 1-H), 6.88-7.38 (m, 10 H, arom); 13C
NMR δ 22.2 (4-CH3); 74.9 (3-CH); 116.6 (2′′,6′′-CH), 121.2 (4′′-
CH), 127.1 (2′′,5′′-CH), 128.1 (CH), 129.0 and 129.8 (2′,3′,5′,6′-
CH), 131.1 (CH), 131.2 (CH), 137.0 (1′-C), 158.5 (1′′-C); MS
(FAB) m/z (%) 224 (8, M•+), 131 (100).
Rea r r a n gem en t of (R)-(+)-102 in th e P r esen ce of
Lew is-Acid Ca ta lysts. Meth od A. A solution of (R)-(+)-102
(70 mg, 0.31 mmol) in CH2Cl2 (5 mL) was treated with the
catalyst B as described in the General Procedure for Allylic
Substitution. After 20 h at room temperature, the usual
workup afforded a 50:50 mixture of 38 and 41 (29 mg, 42%)
identical with the compounds prepared directly from 7 and
27 (see above). GC-MS analysis of the crude product mixture
showed the presence of phenol (∼5%). The mixture exhibited
no optical rotation.
Meth od C. Following the literature procedure,24 a solution
of (R)-(+)-104 (35 mg, 0.13 mmol) in CH2ClCH2Cl (0.5 mL)
was treated with Eu(fod)3 for 12 h at 80 °C to afford 106 (16
mg, 46%) as a 4:1 mixture of trans/ cis-isomers. The trans-iso-
mer was separated from the mixture by preparative HPLC on
Partisil 10 column with a 95:5 mixture hexanes-ethyl acetate.
(E)-1-P h en yl-1-(2′′-h yd r oxyn a p h t h yl)-2-b u t en e (106):
1H NMR δ 1.77 (d, J ) 6.3 Hz, 3 H, 4-Me), 5.6 (m, 2 H, 1,3-H),
5.83 (s, 1H, OH), 6.20 (ddq, J ) 15.4, 6.3, 1.6 Hz, 1 H, 2-H),
7.08-7.93 (m, 11 H, arom); 13C NMR δ 18.4 (4-CH3); 45.6 (1-
CH); 119.7 (CH), 119.8 (C), 123.2 (CH), 123.5 (CH), 127.0 (CH),
127.2 (CH), 128.5 and 129.2 (2′,3′,5′,6′-CH), 129.3 (CH), 129.7
(CH), 130.0 (C), 130.3 (CH), 132.1 (CH), 133.4 (C), 141.9 (C),
153.0 (2′′-C); MS (EI) m/z (%) 274 (100, M•+). HPLC on
Chiralcel OD-H column with a 95:5 hexane-2-propanol mix-
ture showed 82% ee (tmajor ) 15.8 min, tminor ) 14.6 min; flow
rate 0.5 mL/min).
Meth od B. A solution of (R)-(+)-102 (60 mg, 0.27 mmol) in
CH2Cl2 (5 mL) was treated with Yb(OTf)3 for 20 h at room
temperature to afford a ∼50:50 mixture of 38 and 41 (26 mg,
43%) with no optical rotation.
Meth od C. Following the literature procedure,24 a solution
of (R)-(+)-102 (70 mg, 0.31 mmol) in CH2ClCH2Cl (0.5 mL)
was treated with Eu(fod)3 at 80 °C for 12 h to afford 103 (34
mg, 49%) as a 4:1 mixture of trans/ cis-isomers and unreacted
starting material (17 mg, 24%).
1-P h en oxycycloh ex-1-en e (107).38 To a stirred solution
of cyclohex-2-en-1-ol (500 mg, 5.10 mmol), phenol (27) (590 mg,
6.27 mmol), and triphenylphosphine (1.638 g, 6.25 mmol) in
THF (30 mL) at -20 °C was added dropwise diethyl azodicar-
boxylate (1.088 g, 6.25 mmol). The reaction mixture was
allowed to warm to room temperature and the stirring
continued for 4 h. The solvent was removed under reduced
pressure, and the residue was extracted with hexane (3 × 20
mL). The hexane solution was concentrated in vacuo and
passed through a silica gel column (15 × 2 cm) with a 9:1
hexanes-ethyl acetate mixture as eluent to furnish the ether
107 (680 mg, 77%): 1H NMR δ 1.55-2.18 (m, 6 H, 3 × CH2),
4.78 (m, 1 H, 3-H), 5.80 (dm, J ) 10.1 Hz, 1 H, 2-H), 6.04 (dt,
J ) 10.1, 3.5 Hz, 1 H, 1-H), 6.90 (m, 3 H, 2′-H, 4′-H, 6′-H),
7.26 (t, J ) 8.5 Hz, 2 H, 3′-H, 5′-H); 13C NMR δ 19.5, 25.5,
28.8 (4,5,6-CH2), 71.2 (3-CH), 116.3 (2′,6′-CH), 121 (4′-CH),
126.9 and 132.5 (1,2-CH), 129.9 (3′,5′-CH), 158.3 (1′-C). MS
(EI) m/z (%) 174 (0.7, M•+), 80 (100).
Rea r r a n gem en t of th e Eth er 107 in th e P r esen ce of
th e Ca ta lyst B. Treatment of 107 (100 mg, 0.57 mmol) with
the catalyst B (5 mol %) for 20 h afforded a multiproduct mix-
ture. The major components of the mixture were separated
by column chromatography on silica gel (15 × 2 cm) with a
9:1 hexanes-ethyl acetate mixture as eluent and identified
as follows (in order of elution): the starting material 107 (15
mg, 15%), 1-(2′-hydroxyphenyl)cyclohex-2-ene (71) (36 mg,
36%), identical with the compound prepared directly from 17
and 27 (see above), and 3-(4′-hydroxyphenyl)cyclohexene39 (10
mg, 10%). The GC-MS analysis of the crude product mixture
also showed the presence of several poly-allylated products and
phenol (∼5%). 1-(4′-Hydroxyphenyl)cyclohex-1-ene:39 1H NMR
δ 1.50-2.18 (m, 6 H, 3 × CH2), 3.28 (m, 1 H, 3-H), 4.65 (s, 1
H, OH), 5.68 (dm, J ) 10.1 Hz, 1 H, 2-H), 5.86 (ddd, J ) 10.1,
6.0, 3.4 Hz, 1 H, 1-H), 6.75 (d, 2 H, 2′-H, 6′-H), 7.07 (d, 2 H,
3′-H, 5′-H).
(E)-1-P h en yl-1-(2′′-h yd r oxyp h en yl)-2-bu ten e ((E)-103):
1H NMR δ (taken in a mixture with the (Z)-isomer) 1.75
28,37b
(d, J ) 6.3 Hz, 3 H, 4-Me), 4.86 (m, 2 H, 3-H and OH), 5.49
(qdd, J ) 15.4, 6.6, 1.3 Hz, 1 H, 3-H), 5.95 (ddq, J ) 15.4, 7.1,
1.6 Hz, 1 H, 2-H), 6.79-7.34 (m, 9 H, arom), in accordance
with the literature. HPLC on Chiralcel OD-H column with a
98.5:1.5 hexane-2-propanol mixture showed 76% ee (tmajor
)
25.7 min; the minor enantiomer had tminor ) 25.0 min; flow
rate 0.5 mL/min).
(Z)-1-P h en yl-1-(2′′-h yd r oxyp h en yl)-2-bu ten e ((Z)-103):
1H NMR δ (taken in a mixture with the (E)-isomer) 1.73 (d, J
) 6.6 Hz, 3 H, 4-Me), 5.20 (d, 1 H, J ) 9.5 Hz, 3-H), 5.49 (qd,
J ) 10.9, 7.1 Hz, 1 H, 3-H), 5.89 (m, 1 H, 2-H), 6.79-7.34 (m,
9 H, arom). HPLC analysis on Chiralcel OD-H column (98.5:
1.5 hexane-2-propanol) of a sample containing mainly the (E)-
isomer showed g80% ee, but the low content of the (Z)-isomer
did not allow us to determine its ee accurately (tmajor ) 31.5
min; tminor ) 30.5 min; flow rate 0.5 mL/min).
(R)-(+)-1-P h en yl-3-(2-n a p h th oxy)-1-bu ten e (104) was
prepared by following the literature procedure11 from carbon-
ate (R)-(+)-101 (150 mg, 0.68 mmol) and 2-naphthol (100 mg,
0.69 mmol) in 86% yield (161 mg, 0.59 mmol): [R]D +233.3 (c
1
2.0, CHCl3); H NMR δ 1.54 (d, J ) 6.6 Hz, 3 H, 4-Me), 5.06
(p, J ) 6.3 Hz, 1 H, 3-H), 6.30 (dd, J ) 16.4, 6.0 Hz, 1 H, 2-H),
6.63 (d, J ) 16.1 Hz, 1 H, 1-H), 7.12-7.72 (m, 12 H, arom);
13C NMR δ 22.2 (4-CH3); 75.0 (3-CH); 109.6 (CH), 120.1 (CH),
124.2 (CH), 126.8 (CH), 127.0 and 129.1 (2′,3′,5′,6′-CH), 127.3
(CH), 128.1 (CH), 128.3 (CH), 129.5 (C), 129.9 (CH), 131.1
(CH), 131.2 (CH), 135.1 (C), 137.0 (C), 156.4 (2′′-C); MS (EI)
m/z (%) 274 (12, M•+), 131 (100).
Rea r r a n gem en t of (R)-(+)-102 in th e P r esen ce of
Lew is-a cid Ca ta lysts. Meth od A. A solution of (R)-(+)-104
(30 mg, 0.11 mmol) in CH2Cl2 (5 mL) was treated with the
catalyst B. After 8 h at room temperature, the usual workup
afforded 105 (21 mg, 70%).
Ack n ow led gm en t. We thank the EPSRC for Grants
No. GR/H92067 and GR/K07140, EPSRC and Glaxo-
Wellcome PLC for a CASE award to S.L.D., and AgrEvo
Ltd. for additional support.
1-P h en yl-3-(2′′-h yd r oxyn a p h th yl)-1-bu ten e (105): 1H
NMR δ 1.63 (d, J ) 6.9 Hz, 3 H, 4-Me), 4.64 (q, J ) 6.9 Hz, 1
H, 3-H), 5.87 (s, 1H, OH), 6.74 (s, 2 H, 1, 2-H), 7.04-8.05 (m,
11 H, arom); 13C NMR δ (acetone-d6) 19.8 (4-CH3); 35.3 (3-
CH); 119.8 (CH), 123.7 (CH), 124.1 (C), 124.9 (CH), 127.1 (CH),
127.3 and 129.7 (2′,3′,5′,6′-CH), 128.0 (CH), 129.4 (CH), 129.5
(CH), 130.1 (CH), 130.9 (C), 134.4 (C), 136.7 (CH), 139.4 (C),
153.5 (2′′-C); MS (EI) m/z (%) 274 (100, M•+). GC-MS analysis
of the crude product mixture showed the presence of naphthol
(∼5%). The product had no optical rotation and HPLC on
Chiralcel OD-H column with a 95:5 hexane-2-propanol mix-
ture revealed equal amounts of the two enantiomers (t ) 17.2
min and t ) 18.4 min; flow rate 0.5 mL/min).
Su p p or tin g In for m a tion Ava ila ble: MS and HRMS
spectral characteristics and elemental analyses for new com-
1
pounds and H and 13C NMR spectra for the new compounds.
This material is available free of charge via the Internet at
http://pubs.acs.org.
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