Allylindation of 6-substituted 2-hydroxy-l-tetralones in aqueous and organic media. stereochemistry and competition studies

Article abstract of DOI:10.1021/jo980825f

A systematic investigation of the stereoselectivity associated with coupling reactions involving the allylindium reagent and 6-substituted 2-hydroxy-l-tetralones is presented. In each instance, the allylations were carried out in water, 50% aqueous THF, a

Full text of DOI:10.1021/jo980825f

6
990
J . Org. Chem. 1998, 63, 6990-6998
Allylin d a tion of 6-Su bstitu ted 2-Hyd r oxy-1-tetr a lon es in Aqu eou s
a n d Or ga n ic Med ia . Ster eoch em istr y a n d Com p etition Stu d ies
Paul C. Lobben and Leo A. Paquette*
Evans Chemical Laboratories, The Ohio State University, Columbus, Ohio 43210
Received May 1, 1998
A systematic investigation of the stereoselectivity associated with coupling reactions involving the
allylindium reagent and 6-substituted 2-hydroxy-1-tetralones is presented. In each instance, the
allylations were carried out in water, 50% aqueous THF, and dry THF. The extent of 1,2-induction
2
was found to be highest in THF-H O (1:1) and to favor the trans diol isomer. Somewhat lower
levels of stereochemical bias in the same direction were observed in pure water. However, further
erosion of this trend was noted for those reactions performed in THF, such that a modest crossover
in product distribution became apparent in certain examples. On the basis of competition
experiments, both reaction trajectories give evidence of proceeding via chelated intermediates. The
extent of stereoinduction was found to be in line with the normal predilection of 2-cyclohexenones
for axial attack, which is the process believed to be beset with minimal torsional effects. The
substituents situated para to the ketone carbonyl do not exert a very large influence on product
distribution, although electronic effects are evident in the context of the competition studies. A
mechanistic model which integrates these findings is offered.
During the past several years, we have been concerned
Sch em e 1
with the development of new stereoselective reactions
relevant to indium-mediated allylations performed in
water.1 One aspect of these studies has focused on the
ability of unprotected hydroxyl groups to direct carbon-
carbon bond formation as a consequence of chelation to
the organometallic reagent in an aqueous environment.
Where aldehydes are involved, R- or â-oxy substitution
such as in 1 and 2 promotes very good diastereofacial
control to deliver syn-1,2-diols and anti-1,3-diols, respec-
tively, as illustrated in Scheme 1.2 In 2-hydroxycyclo-
hexanones such as 3, the neighboring hydroxyl substit-
uent very effectively controls the stereochemical outcome
of those coupling processes performed in water, irrespec-
tive of whether it resides in an axial or equatorial
disposition.3 In all three series, the allylations are
accelerated, as anticipated if chelated intermediates
intervene.4 In fact, the reactivity of 3b suggests that the
effects of steric screening in the vicinity of the OH group
on the reactivity of the allylindium reagent is virtually
inconsequential.
transition states, and (d) para substituent contributions
to chelation control and the nucleophilic addition process.
It is widely recognized that for 4-substituted cyclo-
hexenes the equatorial conformer is more stable than the
axial one.5 By analogy, 4e should be favored over 4a .
Furthermore, if the conformational dynamics of 2-meth-
oxycyclohexanone serve as a reliable parallel, the en-
thalpy difference between these structures should also
be at a modest level.6 Since intramolecular hydrogen
bonding is likely to be operative in both geometries, this
phenomenon is not expected to introduce any significant
bias.
As a natural extension of these studies, we have
pursued a complementary investigation aimed at subject-
ing 6-substituted 2-hydroxy-1-tetralones to comparable
scrutiny. The fusion of a benzene ring to an R-hydroxy-
cyclohexanone in this manner brings into existence a
number of relevant structural issues that have previously
been accorded little attention. These include (a) ground-
state conformational preferences, (b) steric effects on
chelation capability, (c) A1 strain considerations involv-
ing the ortho aromatic position in the two competing
,3
The steric requirements imposed on intramolecular
chelation to an allylindium species as depicted in 5 and
(
1) Paquette, L. A. In Green Chemistry: Frontiers in Benign Chemi-
cal Synthesis and Processing; Anastas, P.. Williamson, T., Eds.; Oxford
University Press: Oxford, 1998; pp 250-264.
(2) Paquette, L. A.; Mitzel, T. M. J . Am. Chem. Soc. 1996, 118, 1931.
(3) Paquette, L. A.; Lobben, P. C. J . Org. Chem. 1998, 63, 5604.
(4) (a) Chen, X.; Hortelano, E. R.; Eliel, E. L.; Frye, S. V. J . Am.
(5) Lambert, J . B. In The Conformational Analysis of Cyclohexenes,
Cyclohexadienes, and Related Hydroaromatic Compounds; Rabideau,
P., Ed.; VCH: New York, 1989; pp 47-63.
(6) Fraser, R. R.; Faibish, N. C. Can. J . Chem. 1995, 73, 88 and
relevant references therein.
Chem. Soc. 1990, 112, 6130. (b) Frye, S. V.; Eliel, E. L.; Cloux, R. J .
Am. Chem. Soc. 1987, 109, 1862.
S0022-3263(98)00825-1 CCC: $15.00 © 1998 American Chemical Society
Published on Web 09/02/1998

Allylindanation of 6-Substituted 2-Hydroxy-1-tetralones
J . Org. Chem., Vol. 63, No. 20, 1998 6991
Sch em e 2
Sch em e 3
Sch em e 4
6
are distinguishable on an a priori basis (Scheme 2).
When the OH group is oriented in the equatorial plane,
congestion in the vicinity of the binding hydroxyl and
ketonic centers is recognized to be well tolerated.3
Alternative projection of the OH group into the somewhat
more crowded axial region present in cyclohexane frame-
works does not curtail chelation. However, for coordina-
tion to be most effective, a twist-boat conformation must
be adopted at an added energetic cost. These consider-
ations suggest that 5 might be more accessible than 6.
Superimposition of electronic effects from X could serve
to complicate matters. As the 6-substituent is made
increasingly electron-withdrawing, intramolecular hy-
drogen bonding in 4 becomes less influential and has a
corresponding consequence on the 4e a 4a equilibrium.
Resu lts
Syn th etic Con sid er a tion s. The 2-hydroxy-1-tetral-
ones 9 and 10 were obtained by Rubottom oxidation of
the commercially available ketone precursors (Scheme
3). When attempts to implement the same conversion
8
9
The actual nucleophilic addition to the carbonyl group
presents further interesting differences. As the geomet-
ric organization develops in 5, the allyl group needs to
access a region proximate to the ortho C-H bond of the
with 11 were found not to be promising, the Moriarty
protocol10 was used to give 12 in 70% yield.
The N-methylacetamido derivative 18 proved more
difficult to prepare. Sequential N-methylation and chro-
neighboring benzene ring. A1 strain is certain to exert
a rate-retarding effect. The directionality of attack in 6
avoids this particular interaction but is faced with
complementary steric compression arising from the need
to move the developing C-O‚‚‚In functionality out of the
pseudoequatorial plane. Of course, inductive and solvent
polarity forces will have a role to play in all of this. For
example, the inductive effect of the R-hydroxyl substitu-
ent is likely to contribute to higher reactivity of the
carbonyl group.
,3
7
mic acid oxidation of 13 afforded ketone 15 (Scheme
4). In contrast to the other tetralones, 15 proved to be
resistant to an array of R-hydroxylation procedures. As
a result, recourse was made to Wittig olefination in
advance of selenium dioxide oxidation.13 This last step
furnished 17 in 79% yield and set the stage for ozonolytic
11
12
3
cleavage of the exocyclic double bond. As expected, the
H and C NMR spectra of 15-18 were complicated by
1
13
(8) Rubottom, G. M.; Gruber, J . M. J . Org. Chem. 1978, 43, 1599.
(
9) Giardina, G.; Clarke, G. D.; Dondio, G.; Petrone, G.; Sbacchi,
M.; Vecchietti, V. J . Med. Chem. 1994, 37, 3482.
10) (a) Moriarty, R. M.; Engerer, S. C.; Prakash, O.; Prakash, I.;
Gill, U. S.; Freeman, W. A. J . Org. Chem. 1987, 52, 153 and references
therein. (b) Irie, H.; Matsumoto, R.; Nishimura, M.; Zhang, Y. Chem.
Pharm. Bull. 1990, 38, 1852.
(11) Stork, G. J . Am. Chem. Soc. 1947, 69, 576.
12) Allinger, N. L.; J ones, E. S. J . Org. Chem. 1962, 27, 70.
13) Sharpless, K. B.; Lauer, R. F. J . Am. Chem. Soc. 1973, 95, 7917;
The experiments to be described were undertaken to
assess the level at which these stereodifferentiated
reactions operate as X is modified from methoxy to cyano
and as the solvent system is changed from pure water
and 50% aqueous tetrahydrofuran to anhydrous THF.
(
(
(
(7) J ohnson, F. Chem. Rev. 1968, 68, 375.
1972, 94, 7154.

6
992 J . Org. Chem., Vol. 63, No. 20, 1998
Lobben and Paquette
Ta ble 1. In d iu m -P r om oted Allyla tion s of 2-Hyd r oxy-1-tetr a lon es in Va r iou s Solven ts (CH2dCHCH2Br , 25 °C)a
product ratio
entry
carbonyl reactant
9 (X ) H)
solvent
reactn time, h
cis
trans
yield, %
1
2
3
H2O
1.5
1.5
144
1
1
1.7
2.5
3.8
1
82
95
72
H2O-THF (1:1)
THF
4
5
6
10 (X ) OCH3)
H2O
H2O-THF (1:1)
THF
1.5
1.0
36
1
1
2.4
3.0
4.4
1
76
91
63
7
8
9
12 (X ) Br)
H2O
H2O-THF (1:1)
THF
1.0
0.5
10
1
1
1
4.5
5.8
1.5
89
93
78
1
1
1
1
0
1
2
3
18 (X ) N(CH3)COCH3)
H2O
2.0
3.0
120
1
1
1.5
4.0
no reaction
69
94
H2O-THF (1:1)
THF
THFb
<0.5
1
2.6
81
1
1
1
1
4
5
6
7
22 (X ) CN)
H2O
2.0
1.5
120
0.5
1
1
3.2
6.3
90
90
H2O-THF (1:1)
THF
no reaction
1.6
THFb
1
88
a
All of the reactions were performed at least in duplicate at a concentration of 0.1 M with vigorous stirring for the indicated time span.
The THF solution of allyl bromide was heated to reflux with the indium powder for 10 min under N2 and then cooled to rt prior to the
b
introduction of the R-hydroxytetralone.
Sch em e 5
Sch em e 6
the presence of different amide rotamers in an ap-
proximately 2:1 ratio.
The straightforward nature and overall ease of opera-
tion of the preceding synthetic sequence proved to be
sufficiently attractive to encourage its adaptation to the
1
2
cyano derivative. In this instance, the known ketone 19
was transformed satisfactorily via 20 and 21 into 22
(Scheme 5).
Allyla tion Ster eoselectivity. The results obtained
with the five available R-ketols are summarized in Table
. The product diols 23 and 24 (see Scheme 6) were
1
separated chromatographically, and their stereochemis-
tries were revealed by conversion to their carbonates 25
and 26 with 1,1′-carbonyldiimidazole (CDI) followed by
NOE difference experiments on these cyclic derivatives
field aromatic proton H-8 in the two isomers (see Ex-
perimental Section). Particularly striking is the very
long elapsed time needed to consume all of 9 when water
is absent from the reaction medium. This substantive
rate difference was found to persist throughout the entire
study.
A very similar crossover in diastereoselectivity was
observed for the methoxy-substituted example 10 (entries
4-6). Once again, the use of 50% aqueous THF led to
the formation of the highest proportion (4.4:1) of trans
diol, i.e., 24b. While our expectation was that the
(consult Experimental Section). The yields in entries
1
-17 range from good to excellent.
The data recorded for parent system 9 (entries 1-3)
provide important calibration points suitable for com-
parison with the substituted derivatives. The trans diol
2
4a is seen to predominate in water and aqueous THF,
reaching a maximum of 3.8:1 in the mixed-solvent
system. However, the diastereoselectivity realized in
THF is reversed in favor of 23a , which now dominates
1
by a factor of 1.7:1 as determined by H NMR integration
3
electron-donating ability of p-OCH would retard the
of unpurified reaction mixtures. This technique was
utilized in all of the cases examined here in light of the
diagnostic differences in the chemical shifts of the down-
indium-promoted coupling to allyl bromide, this effect
was not observed. In fact, coupling to 10 proceeded four
times faster (as judged by the amount of time required

Allylindanation of 6-Substituted 2-Hydroxy-1-tetralones
J . Org. Chem., Vol. 63, No. 20, 1998 6993
Ta ble 2. Com p etitive In d iu m -P r om oted Allyla tion s in Wa ter a t 25 °C (see Sch em e 6)a
a
All experiments were conducted minimally in duplicate except where noted, and the reported data represent the average of these
b
1
experiments. Relative rate ratios were determined by quantitative analysis via H NMR spectroscopy of the unreactive tetralones present
in the unpurified reaction mixtures. Single-trial experiments.
c
to consume the starting material completely) than the
parallel reaction involving 9 in dry THF (entry 6). This
apparent anomaly foreshadowed related observations to
be described below.
days (entry 12). The latter result is to be contrasted with
the data contained in entries 3, 6, and 9. When recourse
was made instead to preformation of the allylindium
reagent by heating allyl bromide with indium powder
The bromo-substituted derivative 12 responded well
to the allylindium reagent under the trio of reaction
conditions (entries 7-9). Although trans diol 24c pre-
dominated in all three solvent environments, its propor-
tion in the anhydrous THF runs was a factor of 4 less
than the maximum of 5.8:1 encountered in aqueous THF,
and this magnitude of change was entirely consistent
with that encountered in the other cases. In other words,
the behavior of 12 does not deviate from the typical trend
in which the aqueous THF procedure delivers 20-30%
more of 24 relative to the experiment involving pure
water as solvent and a 4- to 6-fold increase in the
proportion of this isomer relative to the THF protocol.
N-Methylacetamido substitution as in 18 resulted in
somewhat slower allylation in aqueous media (entries 10
and 11) and no detectable coupling in dry THF after 5
2
under N for 10 min prior to the introduction of 18 at
room temperature, rapid C-C bond formation ensued to
deliver trans diol 26d with modest diastereoselectivity
(entry 13). This was the first time that the amount of
trans diol produced in THF alone exceeded (by ap-
proximately a factor of 2) that generated in water.
Although the cyano example 22 afforded homoallylic
alcohols 23e and 24e smoothly (entries 14 and 15), again
no reaction was noted in dry THF after 5 days (entry 16).
Thus, the pattern of reactivity exhibited when an electron-
withdrawing group is oriented para to the carbonyl is
seemingly to curtail coupling under these conditions. In
contrast, preformation of the organometallic reagent
leads to the rapid consumption of 22 (entry 17). The
diastereomeric ratios exhibited by the cyano derivative
are quite normal.

6
994 J . Org. Chem., Vol. 63, No. 20, 1998
Lobben and Paquette
Ta ble 3. Com p etitive In d iu m -P r om oted Allyla tion s in THF -H2O (1:1) a t 25 °Ca
a,b
See footnotes to Table 2.
Com p etition Exp er im en ts. To gauge the relative
coupling becomes increasingly advanced. Accompanying
these changes is a significant decrease in the pH of the
medium from 7 to about 4.2 This feature of indium
catalysis leads to an acceleration of product formation
as time elapses.
reactivities of the 6-substituted 2-hydroxy-1-tetralones
more accurately, two series of competition experiments
were performed in which a pair of ketones was allowed
to vie for a limited amount of the allylindium reagent to
the point of its total consumption. In the first, water
alone was utilized as the reaction solvent (Table 2).
Because solubility factors constitute an added kinetic
criterion under these circumstances, a different slate of
competitive allylations was performed in 50% aqueous
THF, where substrate solubility was not a concern (Table
When an organic cosolvent was used as in entries 26-
29 and 22 was allowed to compete directly with the other
four hydroxytetralones (Table 3), a trend not dissimilar
from that found in Table 2 was noted. Although the
cyano derivative proved to be significantly more reactive
than the methoxy example, a nearly identical 2:1 rate
ratio was manifested in the remaining three cases. Since
micelle formation is not encountered in this medium,
further consideration of this issue may not be warranted.
Instead, the damping of those factors that might give rise
to a greater spread in reactivity can conceivably arise
because of the operation of a single electron-transfer
mechanism.
3
). If chelation holds importance, more rapid conversion
to product is expected because of a lowering of transition-
state energy requirements stemming from preformation
of the complex.4 In addition, the neighboring coordinated
hydroxyl group should prove conducive to stereocon-
trolled delivery of the allyl residue as depicted earlier in
5
and 6.
Entries 18 and 19 hold interest in that the R-hydrox-
ytetralones are seen to exhibit reactivity 5-fold greater
than that of the less functionalized R-tetralones. This
trend has been substantiated by means of independent
experiments involving the individual pure ketones and
therefore cannot be attributed to any great degree to
differential solubility in water. Beyond this, entries 20-
Discu ssion
The 1,2-addition of a variety of sterically undemanding
nucleophiles to 2-cyclohexenones is widely recognized to
proceed with substantially enhanced axial stereoselec-
tivity relative to cyanohexanones.
theoretical studies, Houk and co-workers have accounted
14,15
On the basis of
2
5 establish the hierarchy for relative reactivity to be of
)COCH > OCH Thus,
the order H ∼ Br ∼ N(CH
3
3
3
.
although inductive effects are observed, they are of a low
order of magnitude. Similarly, the equally competitive
natures of the protio, bromo, and N-methylacetamido
derivatives relative to the methoxy tetralone are very
telling in their variance from any reasonable quantitative
effect of structure on reactivity.
(
14) Toromanoff, E. In Topics in Stereochemistry; Allinger, N. L.,
Eliel, E. L., Eds.; Interscience: New York, 1967; Vol. 2, p 157.
15) (a) Hennion, G. F.; O’Shea, F. X. J . Am. Chem. Soc. 1958, 80,
14. (b) Baldwin, J . E. J . Chem. Soc., Chem. Commun. 1976, 738. (c)
Kienzle, F.; Mayer, M. Helv. Chim. Acta 1978, 61, 2609. (d) Caine, D.;
Smith, T. L., J r. J . Am. Chem. Soc. 1980, 102, 7568. (e) Findlay, J . A.;
Desai, D. N.; Lonergan, G. C.; White, P. S. Can. J . Chem. 1980, 58,
827. (f) Kuwajima, I.; Nakamura, E.; Hashimoto, K. Tetrahedron
983, 39, 975. (g) Stork, G.; Stryker, J . M. Tetrahedron Lett. 1983, 24,
4887. (h) Fleming, I.; Terreth, N. K. J . Organomet. Chem. 1984, 264,
(
6
2
1
The lack of correlation could be due to the complex
manner in which most indium-promoted allylations occur
in water. As the reaction proceeds, globular micelles
make their appearance and are gradually replaced by a
milky white, inorganic suspension as the extent of
9
1
1
9. (i) Trost, B. M.; Florez, J .; J ebaratnam, D. J . J . Am. Chem. Soc.
987, 109, 613. (j) Idrissi, M. E.; Santelli, M. J . Org. Chem. 1988, 53,
010. (k) Trost, B. M.; Florez, J .; Haller, K. J . J . Org. Chem. 1988, 53,
2394.

Allylindanation of 6-Substituted 2-Hydroxy-1-tetralones
J . Org. Chem., Vol. 63, No. 20, 1998 6995
for this kinetic preference in terms of torsional effects
operational in the transition-state structures.16 As a
as a solution in THF (80 mL). The reaction mixture was
subsequently warmed to room temperature during 12 h,
diluted with triethylamine (75 mL), and concentrated in vacuo.
The residual solid was slurried in pentane and filtered through
Celite. Concentration of the filtrate under reduced pressure
and subsequent distillation of the resulting crude oil afforded
consequence of the fact that the enone subunit of the
structure remains more nearly coplanar during axial
addition, the associated near-perfect staggering contrasts
with the costly eclipsing that necessarily develops during
equatorial approach. Typical axial selectivities are on
the order of 20:1.15
Comparable stereocontrolling effects can be expected
to operate during carbanion additions to simple R-tetral-
ones, although we are unaware of any diagnostic studies
that would confirm this assumption. The introduction
of an R-hydroxy substituent as in 4 has the effect of
directing attention to two quite different conformations
3
.13 g (92%) of the silyl enol ether intermediate as a slightly
yellow oil: bp 83 °C, 0.4 mmHg.
m-Chloroperbenzoic acid (2.96 g, 17.2 mmol) was cautiously
added to a solution of the silyl enol ether (3.13 g, 14.3 mmol)
in CH
2 2 2
Cl (72 mL) under N . The reaction mixture was stirred
at room temperature for 14 h, washed with saturated NaHCO
3
solution, dried, and concentrated. Tetra-n-butylammonium
fluoride (14.3 mL of a 1.0 M solution in THF, 14.4 mmol) was
added to a solution of the resulting crude oil in THF (55 mL).
The mixture was stirred at room temperature for 12 h, diluted
rather than one. Of these, 4e can be regarded as more
3
with a saturated NaHCO solution, and shaken with ether.
stable than 4a for the usual reasons.5 In structure 4a ,
The separated organic layer was washed with 2 N HCl and
brine, dried, and concentrated. The residue was purified by
flash chromatography on silica gel (elution with 33% ethyl
acetate in hexanes) to afford 2.09 g (83%) of 9 as a light tan
the axial positioning of the sterically bulky OH group
should serve to deter a syn attack at the neighboring
carbonyl unless chelation operates. All indications point
to a similar state of affairs in 4e.
-1
1
solid: mp 39-40 °C; IR (neat, cm ) 3474 (br), 1682; H NMR
(
300 MHz, CDCl ) δ 8.01 (d, J ) 7.8 Hz, 1H), 7.50 (ddd, J )
3
Since the hydroxyl substituent in 2-hydroxycyclohex-
anones is shown to be eminently capable of engaging
effectively in chelation irrespective of an axial or equato-
7.5, 7.5, 1.2 Hz, 1H), 7.34-7.23 (m, 2H), 4.37 (dd, J ) 13.5,
5.4 Hz, 1H), 3.55 (br s, 1H), 3.13 (ddd, J ) 17.1, 12.7, 4.4 Hz,
1
H), 3.01 (ddd, J ) 17.1, 4.8, 2.6 Hz, 1H), 2.55-2.47 (m, 1H),
13
3
2.02 (dddd, J ) 12.8, 12.8, 12.8, 4.9 Hz, 1H); C NMR (75
MHz, CDCl ) ppm 199.6, 144.3, 134.1, 130.4, 128.9, 127.5,
26.9, 73.8, 31.8, 27.7; HRMS (EI) m/z (M ) calcd 162.0681,
obsd 162.0680.
,4-Dih yd r o-2-h yd r oxy-6-m et h oxy-1(2H )-n a p h t h a le-
rial status, precoordination in the present examples is
3
considered to be highly likely. Entries 18 and 19 support
this conclusion. This mechanistic model allows direct
correlation with the product ratios compiled in Table 1.
In water and 50% aqueous THF, enhanced selectivity is
observed for passage via 6 to the trans diol. The
selectivity for this reaction channel varies from 1.5:1 to
+
1
3
n on e (10). Comparable treatment of 6-methoxy-1-tetralone
(3.52 g, 20.0 mmol) afforded 1.27 g (32%) of 10 as a light tan
solid, mp 85.0-86.5 °C (from hexanes/ethyl acetate): IR (KBr,
-
1
1
cm ) 3477 (br), 1664; H NMR (300 MHz, CDCl ) δ 8.00 (d, J
3
6
.3:1 depending on the nature of X and the percent of
)
8.7 Hz, 1H), 6.85 (dd, J ) 8.7, 2.5 Hz, 1H), 6.70 (d, J ) 2.4
water in the reaction medium. The involvement of 6 is
less dominant in anhydrous THF. In actuality, formation
of the cis diol via 5 is modestly favored when X ) H or
Hz, 1H), 4.31 (dd, J ) 13.3, 5.4 Hz, 1H), 3.85 (s, 3H), 3.10 (dd,
J ) 12.8, 4.4 Hz, 1H), 2.97 (ddd, J ) 17.0, 4.7, 2.6 Hz, 1H),
2
.49 (dddd, J ) 10.4, 5.3, 4.5, 2.6 Hz, 1H), 2.00 (dddd, J )
1
3
OCH
3
. Significant solvent polarity alterations such as
12.9, 12.9, 12.9, 4.8 Hz, 1H); C NMR (75 MHz, CDCl ) ppm
3
those at play here can be expected to have an influence
on stereoselectivity. To understand these results in more
detail, theoretical studies which incorporate solvation
parameters would need to be undertaken.
Further explanation of the findings recorded herein
may prove to be unwarranted at this time. Vedejs has
indicated that although ground-state torsional interac-
tions have complicated origins, all estimates of the
198.1, 164.2, 146.9, 130.0, 123.8, 113.6, 112.7, 73.4, 55.5, 31.8,
+
2
8.0; HRMS (EI) m/z (M ) calcd 192.0787, obsd 192.0785.
Anal. Calcd for C11
H, 6.32.
12 3
H O : C, 68.74; H, 6.29. Found: C, 68.66;
6
-B r o m o -3,4-d ih y d r o -2-h y d r o x y -1(2H )-n a p h t h a le -
-blanketed solution of 119 (0.638 g, 2.84
n on e (12). To a N
2
mmol) in methanol (10.0 mL) at 0 °C was added a methanolic
solution of KOH (2.387 g, 42.5 mmol, 18 mL), followed by
iodobenzene diacetate (1.096 g, 3.40 mmol). As the color
changed from green to orange, the reaction mixture was
warmed to room temperature over 4 h, diluted with brine, and
extracted with ether. The combined organic layers were
washed with 10% HCl and brine, dried, and concentrated. The
residue was purified chromatographically on silica gel (elution
with 10% ethyl acetate in hexanes) to afford 0.476 g (70%) of
torsional energies of developing bonds are quite unreli-
able.17 In the present setting, attempts to separate steric
and electronic factors are problematic. Suffice it to
indicate therefore that a synthetically useful allylindation
process favoring production of the trans diol has been
delineated which is consistent with prior chelation and
preferred C-C bond formation from the axial direction.
-
1
1
12: mp 89-90 °C; IR (KBr, cm ) 3490, 1679; H NMR (300
MHz, CDCl ) δ 7.89 (d, J ) 8.3 Hz, 1H), 7.50-7.46 (m, 2H),
3
4
3
2
.36 (ddd, J ) 13.5, 5.4, 2.0 Hz, 1H), 3.83 (d, J ) 2.0 Hz, 1H),
.14 (ddd, J ) 17.3, 12.8, 4.5 Hz, 1H), 3.00 (ddd, J ) 17.3, 4.7,
.6 Hz, 1H), 2.57-2.48 (m, 1H), 2.03 (ddd, J ) 26.2, 12.9, 4.8
Exp er im en ta l Section 18
1
3
3
Hz, 1H); C NMR (75 MHz, CDCl ) ppm 198.7, 145.9, 131.8,
3
,4-Dih yd r o-2-h yd r oxy-1(2H)-n a p h th a len on e (9). n-
1
30.4, 129.5, 129.1, 73.7, 31.5, 27.4 (one quaternary C not
Butyllithium (15.2 mL of a 1.6 M solution in hexanes, 24.3
mmol) was added at -78 °C to a solution of N,N-diisopropy-
2
lamine (2.84 mL, 20.3 mmol) in THF (78 mL) under N . The
+
observed); HRMS (EI) m/z (M ) calcd 241.9766, obsd 241.9771.
N -Me t h y l-N -(5,6,7,8-t e t r a h y d r o -2-n a p h t h y l)a c e t -
a m id e (14). Sodium hydride (0.72 g, 30 mmol) was added
portionwise to a solution of 1312 (4.73 g, 25.0 mmol) in dry
reaction mixture was slowly warmed to 0 °C over 3 h and was
recooled to -78 °C prior to the addition of 1-tetralone (2.28 g,
benzene (50 mol) under N
mL, 50 mmol) was introduced to the reaction mixture, which
was stirred at 60 °C under N for 12 h before being slowly
2
. After 10 min, methyl iodide (3.1
1
5.6 mmol) and chlorotrimethylsilane (2.57 mL, 20.3 mmol)
2
(
16) (a) Wu, Y.-D.; Houk, K. N.; Trost, B. M. J . Am. Chem. Soc. 1987,
quenched with brine and concentrated. The residue was
partitioned between ether and brine, and the separated
aqueous layer was extracted further with ether before the
combined organic layers were dried and concentrated. The
residue was purified by chromatography on silica gel (elution
with 50% ethyl acetate in hexanes) to afford 4.87 g (96%) of
1
09, 5560. (b) Wu, Y.-D.; Houk, K. N.; Florez, J .; Trost, B. M. J . Org.
Chem. 1991, 56, 3656.
17) Vedejs, E.; Dent, W. H., III; Kendall, J . T.; Oliver, P. A. J . Am.
Chem. Soc. 1996, 118, 3556.
18) For generic experimental details, see: Paquette, L. A.; Lobben,
P. C. J . Am. Chem. Soc. 1996, 118, 1917.
(
(

6
996 J . Org. Chem., Vol. 63, No. 20, 1998
Lobben and Paquette
1
2
4 as an off-white fluffy solid: mp 58-59 °C; IR (KBr, cm-1)
DMSO, T ) 363 K) ppm (complicated by rotamers) 168.7,
167.8, 145.9, 143.4, 142.4, 137.2, 132.3, 129.5, 126.3, 125.6,
124.5, 124.2, 122.7, 108.4, 107.8, 68.6, 68.5, 36.5, 36.4, 31.3,
1
934, 1662; H NMR (300 MHz, CDCl
3
) δ 7.04 (d, J ) 18.7
Hz, 1H), 6.85-6.83 (m, 2H), 3.19 (s, 3H), 2.73 (br s, 4H), 1.83
1
3
+
(s, 3H), 1.79-1.75 (m, 4H); C NMR (75 MHz, CDCl
3
) ppm
31.3, 26.2, 25.9, 21.8, 21.7; HRMS (EI) m/z (M ) calcd 231.1259,
1
2
2
70.5, 141.8, 138.5, 136.6, 130.1, 127.1, 123.8, 37.0, 29.2, 28.8,
obsd 231.1253. Anal. Calcd for C14
Found: C, 72.54; H, 7.39.
2
H17NO : C, 72.70; H, 7.41.
+
2.8, 22.7, 22.2; HRMS (EI) m/z (M ) calcd 203.1310, obsd
03.1312.
N-Meth yl-N-(5,6,7,8-tetr ah ydr o-6-h ydr oxy-5-oxo-2-n aph -
th yl)a ceta m id e (18). A -78 °C solution of 17 (0.502 g, 2.17
mmol) in a 1:1 mixture of CH Cl and methanol (22 mL)
2 2
containing 1% pyridine was ozonolyzed until a faint blue color
persisted (∼20 min) and was quenched with dimethyl sulfide
(0.32 mL). The reaction mixture was warmed to room tem-
N-Meth yl-N-(5,6,7,8-tetr a h yd r o-5-oxo-2-n a p h th yl)a ce-
ta m id e (15). A solution of chromium trioxide (9.99 g, 0.100
mmol) in acetic acid (25 mL) and water (5 mL) was added
dropwise to a chilled (∼10 °C) solution of 14 (5.08 g, 25.0 mmol)
in acetic acid (20 mL). The reaction mixture was warmed to
room temperature over 8 h, cautiously quenched with 50%
2 2
perature over 4 h, diluted with CH Cl , partitioned with brine,
NaHCO
3
solution, and extracted with ether. The combined
and extracted with ethyl acetate. The combined organic layers
were dried and concentrated to leave a residue, which was
purified by column chromatography on Florisil (elution with
75% ethyl acetate in hexanes) to afford 0.376 g (74%) of 18 as
organic layers were dried and concentrated to leave a residue,
which was purified by column chromatography on silica gel
(elution with 50% ethyl acetate in hexanes) to afford 3.71 g
-
1
-1
1
(
3
70%) of 15 as a white solid: mp 104-105 °C; IR (KBr, cm
)
a colorless oil: IR (neat, cm ) 3422 (br), 1688; H NMR (300
MHz, d -DMSO, T ) 363 K) δ 7.91 (d, J ) 8.9 Hz, 2/3H), 7.73
1
490, 1735, 1664, 1602; H NMR (300 MHz, CDCl
3
) δ 8.03 (d,
6
J ) 8.2 Hz, 2/3H), 7.80 (s, 1/3H), 7.27-7.25 (m, 2/3H), 7.10 (d,
(d, J ) 2.3 Hz, 1/3H), 7.48 (dd, J ) 8.2, 2.3 Hz, 1/3H), 7.39 (d,
J ) 8.2 Hz, 1/3H), 7.29-7.27 (m, 4/3H), 4.31 (ddd, J ) 12.0,
4.8, 4.8 Hz, 1H), 4.24 (br s, 1H), 3.21 (s, 2/3 of 3H), 3.18 (s, 1/3
of 3H), 3.09-3.03 (m, 2H), 2.33-2.24 (m, 1H), 2.05-1.93 (m,
1H), 1.91 (s, 2/3 of 3H), 1.84 (s, 1/3 of 3H); 13C NMR (75 MHz,
J ) 2.1 Hz, 1/3H), 7.07 (d, J ) 2.2 Hz, 1H), 3.24 (s, 2/3 of 3H),
3
2
.20 (s, 1/3 of 3H), 2.97-2.93 (m, 2H), 2.65-2.61 (m, 2H) 2.17-
.09 (m, 2H), 1.91 (s, 2/3 of 3H), 1.82 (s, 1/3 of 3H); 13C NMR
3
(75 MHz, CDCl ) ppm (major rotamer signals) 197.0, 170.0,
1
2
3
2
48.5, 146.0, 131.8, 131.4, 128.8, 126.7, 38.8, 37.0, 29.6, 23.0,
2.4 (minor rotamer signals) 197.4, 170.4, 130.3, 125.4, 125.0,
8.7, 29.1, 22.9; HRMS (EI) m/z (M ) calcd 217.1103, obsd
6
d -DMSO, T ) 363 K) ppm (complicated by rotamers) 197.4,
168.8, 148.4, 145.2, 142.8, 142.6, 132.1, 131.6, 129.8, 129.4,
127.7, 126.1, 124.5, 124.1, 72.5, 36.6, 36.4, 31.6, 26.7, 26.4, 22.0,
+
+
17.1104. Anal. Calcd for C13
H
15NO
2
:
C, 71.87; H, 6.96.
21.7; HRMS (EI) m/z (M ) calcd 233.1052, obsd 233.1055.
Found: C, 72.04; H, 7.07.
5,6,7,8-Tetr a h yd r o-5-m eth ylen e-2-n a p h th on itr ile (20).
Potassium hexamethyldisilazide (6.14 mL of a 0.5 M solution
in toluene, 3.07 mmol) was added via syringe to a suspension
of methyltriphenylphosphonium bromide (1.19 g, 3.33 mmol)
N-Met h yl-N-(5,6,7,8-t et r a h yd r o-5-m et h ylen e-2-n a p h -
th yl)acetam ide (16). To a suspension of methyltriphenylphos-
phonium iodide (2.53 g, 6.27 mmol) in THF (3.1 mL) at 0 °C
under N
2
was added potassium hexamethyldisilazide (12.5 mL
in THF (2.5 mL) at 0 °C under N
2
. The reaction mixture was
of a 0.5 M solution in toluene, 6.27 mmol), followed after 10
min by solid 15 (1.24 g, 5.69 mmol), at which time the reaction
mixture changed from a deep yellow color to a ruby red. The
reaction mixture was warmed to room temperature over 4 h,
allowed to warm to room temperature over 1 h and was
1
2
recooled to 0 °C prior to the addition of solid 19 (0.438 g,
2.56 mmol). The reaction mixture, which turned from intense
yellow to very deep purple, was warmed to room temperature
diluted with a saturated NH
4
Cl solution, and extracted with
4
over 4 h, quenched with a saturated NH Cl solution, and
ether. The combined organic layers were washed with brine,
dried, and concentrated. The residue was purified by flash
chromatography on silica gel (gradient elution with 50-66%
ethyl acetate in hexanes) to afford 0.235 g (19%) of unreacted
extracted with ether. The combined organic layers were dried
and concentrated to leave a residue, which was purified by
silica gel chromatography (elution with 17% ethyl acetate in
hexanes) to afford 0.365 g (84%) of 20 as carmine crystals: mp
52-53 °C; IR (KBr, cm ) 1624, 1489, 1406; 1H NMR (300
-
1
1
5 and 0.880 g (72%) of 16 as a white solid: mp 49-51 °C; IR
-
1
1
(KBr, cm ) 1655; H NMR (300 MHz, CDCl
3
) δ 7.64 (d, J )
.3 Hz, 2/3H), 7.41 (d, J ) 2.1 Hz, 1/3H), 7.13 (d, J ) 8.0 Hz,
/3H), 6.96-6.90 (m, 5/3H), 5.46 (s, 2/3H), 5.43 (s, 1/3H), 4.98
MHz, CDCl
3
) δ 7.68 (d, J ) 8.7 Hz, 1H), 7.39 (d, J ) 8.7 Hz,
8
1
1H), 7.38 (s, 1H), 5.58 (s, 1H), 5.12 (s, 1H), 2.84 (t, J ) 6.3 Hz,
1
3
2H), 2.55 (t, J ) 5.9 Hz, 2H), 1.88 (q, J ) 6.2 Hz, 2H);
C
(
2
1
s, 1H), 3.22 (s, 1/3 of 3H), 3.22 (s, 2/3 of 3H), 2.84-2.80 (m,
NMR (75 MHz, CDCl ) ppm 141.9, 139.3, 138.1, 132.9, 129.2,
3
+
H), 2.55-2.51 (m, 2H), 1.91-1.82 (m, 2H), 1.87 (s, 1/3 of 3H),
124.9, 119.0, 111.6, 32.5, 30.1, 23.0; HRMS (EI) m/z (M ) calcd
169.0891, obsd 169.0898.
1
3
3
.86 (s, 2/3 of 3H); C NMR (75 MHz, CDCl ) ppm (complicated
by rotamers) 170.6, 170.5, 143.6, 142.5, 142.4, 142.3, 138.7,
5,6,7,8-Tetr ah ydr o-6-h ydr oxy-5-m eth ylen e-2-n aph th on i-
tr ile (21). tert-Butyl hydroperoxide (1.62 mL of a 4.0 M
solution in CH Cl , 6.48 mmol) was added to a mixture of
2 2
1
1
36.8, 136.1, 134.1, 130.5, 127.2, 125.9, 125.5, 124.4, 122.5,
08.9, 108.8, 37.1, 37.0, 32.9, 32.8, 32.7, 30.3, 30.0, 23.4, 22.3;
+
HRMS (EI) m/z (M ) calcd 215.1310, obsd 215.1313. Anal.
salicylic acid (30 mg, 0.22 mmol) and selenium dioxide (12 mg,
Calcd for C14
H
17NO: C, 78.10; H, 7.96. Found: C, 77.94; H,
0.11 mmol), followed by a solution of 20 (0.365 g, 2.16 mmol)
7
.94.
in CH
temperature for 12 h, diluted with CH
successively with 10% KOH and 50% K CO
separated aqueous layers were individually extracted with
CH Cl , and the combined organic layers were dried and
2
Cl
2
(2.7 mL). The reaction mixture was stirred at room
Cl , and washed
solutions. The
N-Meth yl-N-(5,6,7,8-tetr ah ydr o-6-h ydr oxy-5-m eth ylen e-
-n a p h th yl)a ceta m id e (17). tert-Butyl hydroperoxide (0.411
2
2
2
2
3
2 2
mL of a 4.0 M solution in CH Cl , 1.64 mmol) was added to a
mixture of selenium dioxide (3.0 mg, 23 µmol) and salicylic
acid (6.0 mg, 46 µmol), followed by 16 (96 mg, 0.46 mmol) as
a solution in CH
stirred at room temperature for 4 h, diluted with 10% KOH
solution, and extracted with CH Cl . The combined organic
layers were washed with a 50% K CO solution, dried, and
2
2
concentrated. The residue was purified by column chroma-
tography on silica gel (elution with 33% ethyl acetate in
hexanes) and recrystallized (ethyl acetate/hexanes) to afford
0.218 g (55%) of 21 as an off-white solid: mp 82-84 °C; IR
2 2
Cl (0.46 mL). The reaction mixture was
2
2
-
1
1
2
3
3
(KBr, cm ) 3323 (br); H NMR (300 MHz, CDCl ) δ 7.68 (d, J
concentrated. The residue was chromatographically purified
on silica gel (elution with 65% ethyl acetate in hexanes) to
afford 82 mg (79%) of 17 as a white solid: mp 146-147 °C; IR
) 8.8 Hz, 1H), 7.43 (d, J ) 8.8 Hz, 1H), 7.41 (s, 1H), 5.70 (s,
1H), 5.47 (s, 1H), 4.54 (dd, J ) 7.2, 3.7 Hz, 1H), 3.08 (ddd, J
) 17.2, 6.8, 6.8 Hz, 1H), 2.85 (ddd, J ) 17.2, 6.3, 6.3 Hz, 1H),
-
1
1
13
(
neat, cm ) 3417 (br), 1652; H NMR (300 MHz, d
363 K) δ 7.66 (d, J ) 8.2 Hz, 2/3H), 7.53 (d, J ) 2.1 Hz,
/3H), 7.16 (d, J ) 8.4 Hz, 1/3H), 7.09-7.04 (m, 5/3H), 5.58
d, J ) 14.3 Hz, 1H), 5.32-5.30 (m, 1H), 4.32 (ddd, J ) 8.7,
.7, 1.7 Hz, 1H), 3.73 (br s, 1H), 3.16 (s, 1/3 of 3H), 3.15 (s, 2/3
6
-DMSO, T
3
2.11-1.94 (m, 3H); C NMR (75 MHz, CDCl ) ppm 144.8,
)
1
137.6, 137.2, 132.7, 129.5, 125.7, 118.9, 112.3, 111.1, 70.1, 30.7,
+
25.9; HRMS (EI) m/z (M ) calcd 185.0841, obsd 185.0834.
(
Anal. Calcd for C12
H, 5.94.
H11NO: C, 77.80; H, 5.99. Found: C, 77.56;
1
of 3H), 2.96 (ddd, J ) 17.0, 6.0, 6.0 Hz, 1H), 2.81 (ddd, J )
5,6,7,8-Tet r a h yd r o-6-h yd r oxy-5-oxo-2-n a p h t h on it r ile
(22). A -78 °C solution of 21 (0.254 g, 1.37 mmol) in a 1:1
2 2
mixture of methanol and CH Cl (13.8 mL) containing 10%
1
1
6.8, 5.8, 5.8 Hz, 1H), 2.01-1.91 (m, 1H), 1.83 (s, 2/3 of 3H),
1
3
.82 (s, 1/3 of 3H), 1.83-1.74 (m, 1H); C NMR (75 MHz, d
6
-

Allylindanation of 6-Substituted 2-Hydroxy-1-tetralones
J . Org. Chem., Vol. 63, No. 20, 1998 6997
pyridine (1.4 mL) was ozonolyzed (∼20 min) until the faint
yellow solution gave way to a clear reaction solution. The
reaction mixture was quenched with dimethyl sulfide (0.20 mL,
J ) 13.9, 6.7 Hz, 1H), 2.11 (dddd, J ) 13.3, 6.6, 4.3, 4.3 Hz,
1H), 2.04-1.90 (m, 1H); 13C NMR (75 MHz, CDCl
) ppm 140.4,
3
134.8, 133.8, 128.5, 127.3, 126.3, 125.7, 119.3, 75.1, 74.4, 40.6,
+
2
.7 mmol), warmed to room temperature over 2 h, partitioned
26.8, 26.1; HRMS (EI) m/z (M ) calcd 204.1150, obsd 204.1148.
with brine, and extracted with CH Cl . The combined organic
2
2
Anal. Calcd for C13
H, 7.89.
cis-1-Allyl-1,2,3,4-t et r a h yd r o-6-m et h oxy-1,2-n a p h t h a -
len ed iol (23b ): colorless oil; IR (neat, cm ) 3401 (br);
NMR (300 MHz, CDCl ) δ 7.49 (d, J ) 8.7 Hz, 1H), 6.81 (dd,
J ) 8.7, 2.7 Hz, 1H), 6.60 (d, J ) 2.7 Hz, 1H), 5.77-5.63 (m,
1H), 5.15-5.06 (m, 2H), 3.95 (br s, 1H), 3.78 (s, 3H), 2.94 (ddd,
J ) 17.1, 6.9, 6.9 Hz, 1H), 2.77-2.66 (m, 2H), 2.60-2.53 (m,
16 2
H O : C, 76.44; H, 7.89. Found: C, 76.33;
layers were dried and concentrated. The residue was purified
by column chromatography on Florisil (elution with 33% ethyl
acetate in hexanes) to afford 0.969 g (71%) of 22 as a light
-
1
1
H
-
1
1
yellow solid: mp 133-135 °C; IR (KBr, cm ) 3482, 1692; H
NMR (300 MHz, CDCl ) δ 8.12 (d, J ) 7.9 Hz, 1H), 7.62 (d, J
7.9 Hz, 1H), 7.60 (s, 1H), 4.43 (dd, J ) 13.6, 5.5 Hz, 1H),
.77 (br s, 1H), 3.19 (ddd, J ) 17.4, 5.1, 2.7 Hz, 1H), 3.08 (ddd,
J ) 17.4, 5.1, 2.7 Hz, 1H), 2.61-2.53 (m, 1H), 2.07 (dddd, J )
3
3
)
3
1
3
2H), 2.33 (br s, 1H), 2.04-1.94 (m, 2H); C NMR (75 MHz,
CDCl ) ppm 158.7, 137.5, 133.6, 131.7, 128.8, 118.7, 112.9,
112.7, 73.4, 70.7, 55.2, 44.7, 26.4, 25.9; HRMS (EI) m/z (M )
1
1
2
2.8, 12.8, 12.8, 5.2 Hz, 1H); 13C NMR (75 MHz, CDCl
3
) ppm
3
+
98.4, 144.7, 133.4, 132.8, 130.2, 128.2, 117.7, 117.3, 73.9, 31.3,
+
7.4; HRMS (EI) m/z (M ) calcd 187.0633, obsd 187.0637.
calcd 234.1256, obsd 234.1260. Anal. Calcd for C14
71.77; H, 7.74. Found: C, 71.49; H, 7.74.
18 3
H O : C,
Anal. Calcd for C11
H, 4.90.
9 2
H NO : C, 70.56; H, 4.85. Found: C, 70.51;
tr a n s-1-Allyl-1,2,3,4-t et r a h yd r o-6-m et h oxy-1,2-n a p h -
th a len ed iol (24b): colorless solid; mp 107-108 °C; IR (KBr,
P r ototyp ica l In d iu m -P r om oted Cou p lin gs. A. In Wa -
-
1
1
ter . A mixture of 9 (41 mg, 0.25 mmol), allyl bromide (32 µL,
3
cm ) 3356 (br); H NMR (300 MHz, CDCl ) δ 7.34 (d, J ) 8.7
0
.38 mmol), and indium powder (43 mg, 0.38 mmol) in water
Hz, 1H), 6.76 (dddd, J ) 8.6, 2.7, 0.7, 0.7 Hz, 1H), 6.60 (d, J )
2.7 Hz, 1H), 5.96-5.82 (m, 1H), 5.19-5.11 (m, 2H), 3.96 (dd,
J ) 11.0, 4.2 Hz, 1H), 3.77 (s, 3H), 2.96-2.90 (m, 2H), 2.72
(dddd, J ) 13.9, 8.1, 1.1, 1.1 Hz, 1H), 2.48 (dddd, J ) 13.9,
6.7, 1.2, 1.2 Hz, 1H), 2.11 (dddd, J ) 13.4, 6.6, 4.4, 4.4 Hz,
(2.5 mL) was tightly stoppered and stirred at room tempera-
ture for 1.5 h, producing a milky white solution. The reaction
mixture was diluted with brine, quenched with 10% HCl, and
extracted with ether. In most instances, the 10% HCl quench
was deemed detrimental to the products and its use was
therefore not implemented. After the combined organic layers
were dried and concentrated, the products were separated
chromatographically as described below.
1
3
1H), 1.97 (dddd, J ) 13.4, 11.0, 9.0, 7.9 Hz, 1H); C NMR (75
MHz, CDCl ) ppm 158.7, 136.4, 134.0, 132.8, 127.6, 119.2,
3
112.9, 112.1, 74.7, 74.6, 55.2, 40.8, 27.0, 26.1; HRMS (EI) m/z
+
(M ) calcd 234.1256, obsd 234.1238. Anal. Calcd for
B. In 50% THF . Indium powder (43 mg, 0.38 mmol) was
added to a magnetically stirred solution of allyl bromide (32
µL, 0.38 mmol) and 9 (41 mg, 0.25 mmol) in a 1:1 mixture of
THF and water (2.5 mL). The reaction mixture was stirred
at room temperature for 1.5 h, diluted with brine, quenched
with 10% HCl, and extracted with ether. In several instances,
the 10% HCl was deemed to be detrimental to the products
and was therefore avoided without adverse effects. The
identical workup followed.
C. In An h yd r ou s THF . A THF (2.5 mL) solution of allyl
bromide (32 µL, 0.38 mmol) and 9 (41 mg, 0.25 mmol) with
added indium powder (43 mg, 0.38 mmol) was tightly stop-
pered and was vigorously stirred at room temperature for 6
d. The reaction mixture was diluted with ether, partitioned
with brine, quenched with 10% HCl, and extracted with ether.
An equally effective procedure that avoided the 10% HCl
quench entailed direct filtration of the reaction mixture
through a pipet containing silica gel (elution with ethyl
acetate). The combined organic layers were dried and con-
centrated, and the usual chromatographic purification fol-
lowed.
C
14
H
18
O
3
: C, 71.77; H, 7.74. Found: C, 71.72; H, 7.68.
cis-1-Allyl-6-br om o-1,2,3,4-tetr ah ydr o-1,2-n aph th alen e-
-
1
1
d iol (23c): colorless oil; IR (neat, cm ) 3401 (br); H NMR
(300 MHz, CDCl ) δ 7.44 (d, J ) 8.4 Hz, 1H), 7.34 (dd, J )
8.4, 2.0 Hz, 1H), 7.25 (dd, J ) 3.8, 3.0 Hz, 1H), 5.81-5.67 (m,
1H), 5.14-5.07 (m, 2H), 3.98 (br s, 1H), 2.97 (ddd, J ) 15.4,
7.7, 7.7 Hz, 1H), 2.74 (br s, 1H), 2.71 (ddd, J ) 17.3, 5.8, 5.8
Hz, 1H), 2.61 (dd, J ) 14.3, 7.4 Hz, 1H), 2.49 (dd J ) 14.3, 7.2
Hz, 1H), 2.30 (br s, 1H), 2.06-1.99 (m, 2H); C NMR (75 MHz,
CDCl ) ppm 138.8, 138.0, 133.0, 131.1, 129.5, 129.3, 121.3,
2
119.2, 73.4, 70.5, 45.2, 25.9, 24.7; HRMS (EI) m/z (M - H O)
calcd 266.0129, obsd 266.0137. Anal. Calcd for C13
C, 55.14; H, 5.34. Found: C, 55.18; H, 5.40.
3
1
3
3
+
2
H15BrO :
tr a n s-1-Allyl-6-br om o-1,2,3,4-tetr a h yd r o-1,2-n a p h th a -
-
1
len ed iol (24c): colorless solid; mp 120-121 °C; IR (KBr, cm
3364 (br); H NMR (300 MHz, CDCl ) δ 7.32-7.23 (m, 3H),
5.91-5.76 (m, 1H), 5.20-5.10 (m, 2H), 3.93 (dd, J ) 11.4, 4.4
Hz, 1H), 3.00-2.83 (m, 2H), 2.71 (dd, J ) 13.9, 8.1 Hz, 1H),
2.62 (br s, 1H), 2.58 (br s, 1H), 2.41 (dd, J ) 13.9, 6.8 Hz, 1H),
)
1
3
1
3
2.15-2.06 (m, 1H), 2.02-1.88 (m, 1H); C NMR (75 MHz,
CDCl ) ppm 139.5, 137.1, 133.3, 131.2, 128.8, 128.2, 121.3,
119.8, 74.8, 74.0, 40.4, 26.6, 25.9; HRMS (EI) m/z (M - H O)
2
calcd 266.0129, obsd 266.0096. Anal. Calcd for C13
C, 55.14; H, 5.34. Found: C, 54.90; H, 5.32.
N-(cis-5-Allyl-5,6,7,8-tetr a h yd r o-5,6,-d ih yd r oxy-2-n a p h -
th yl)-N-m eth yla ceta m id e (23d ): pale yellowish oil; IR (neat,
3
cm ) 3420 (br), 1737; H NMR (300 MHz, CDCl ) δ 7.62 (d, J
) 8.3 Hz, 1H), 7.04 (dd, J ) 8.4, 2.0 Hz, 1H), 6.91 (s, 1H),
5.85-5.71 (m, 1H), 5.24-5.06 (m, 2H), 4.03 (br d, J ) 4.2 Hz,
1H), 3.23 (s, 3H), 3.04-2.94 (m, 1H), 2.81-2.45 (series of m,
3H), 2.10-2.04 (m, 2H), 1.87 (d, J ) 3.7 Hz, 3H); C NMR
(75 MHz, CDCl ) ppm (complicated by rotamers); HRMS (EI)
3
+
D. P r efor m a tion of th e Allylin d iu m Rea gen t in THF .
A suspension of indium powder (17 mg, 0.15 mmol) in a THF
solution (1.0 mL) and allyl bromide (13 µL, 0.15 mmol) was
vigorously stirred at the reflux temperature for 15 min under
2
H15BrO :
2
N , ultimately producing a slightly cloudy homogeneous solu-
-
1
1
tion. The reaction mixture was cooled to room temperature
prior to the addition of 18, stirred at room temperature for 30
min, quenched with brine, and extracted with ether. The
predescribed workup ensued.
1
3
ci s-1-Ally l-1,2,3,4-t e t r a h y d r o -1,2-n a p h t h a le n e d io l
-
1
1
(
23a ): colorless oil; IR (neat, cm ) 3406 (br); H NMR (300
MHz, CDCl ) δ 7.58-7.55 (m, 1H), 7.26-7.07 (series of m, 3H),
.79-5.65 (m, 1H), 5.14-5.07 (m, 2H), 3.94 (dd, J ) 6.7, 3.2
Hz, 1H), 2.96 (dd, J ) 17.1, 7.2 Hz, 1H), 2.77-2.50 (series of
3
+
3
m/z (M ) calcd 275.1522, obsd 275.1500.
N-(tr a n s-5-Allyl-5,6,7,8-t et r a h yd r o-5,6,-d ih yd r oxy-2-
n a p h th yl)-N-m eth yla ceta m id e (24d ): faint yellowish oil; IR
5
1
3
-1
1
m, 5H), 2.08-1.90 (m, 2H); C NMR (75 MHz, CDCl
39.6, 135.8, 133.4, 128.5, 127.4, 127.4, 126.4, 118.8, 73.6, 70.7,
3
) ppm
3
(neat, cm ) 3404 (br), 1735; H NMR (300 MHz, CDCl ) δ 7.48
1
4
2
(d, J ) 3.8 Hz, 2/3H), 7.12-6.89 (series of m, 7/3H), 5.95-
5.72 (m, 1H), 5.22-5.02 (m, 2H), 4.03-3.98 (m, 1H), 3.21 (s,
3H), 3.03-2.92 (m, 1H), 2.82-2.35 (series of m, 3H), 2.20-
+
5.0, 26.2, 25.2; HRMS (EI) m/z (M ) calcd 204.1150, obsd
04.1167. Anal. Calcd for C13 C, 76.44; H, 7.89.
16 2
H O :
Found: C, 76.29; H, 7.97.
tr a n s-1-Allyl-1,2,3,4-t et r a h yd r o-1,2-n a p h t h a len ed iol
1.95 (series of m, 2H), 1.84 (s, 3H); 13C NMR (75 MHz, CDCl
3
)
+
ppm (complicated by rotamers); HRMS (EI) m/z (M ) calcd
275.1522, obsd 275.1520.
-
1
(
(
7
5
2
24a ): colorless white solid; mp 91-92 °C; IR (KBr, cm ) 3360
1
br); H NMR (300 MHz, CDCl
3
) δ 7.44-7.39 (m, 1H), 7.23-
cis-5-Allyl-5,6,7,8-tetr ah ydr o-5,6-dih ydr oxy-2-n aph th on i-
-
1
1
.15 (m, 2H), 7.10-7.07 (m, 1H), 5.94-5.80 (m, 1H), 5.18-
tr ile (23e): clear oil; IR (neat, cm ) 3432 (br); H NMR (300
MHz, CDCl ) δ 7.69 (d, J ) 8.1 Hz, 1H), 7.49 (dd, J ) 8.2, 0.8
Hz, 1H), 7.39 (s, 1H), 5.85-5.71 (m, 1H), 5.18-5.08 (m, 2H),
.11 (m, 2H), 3.97 (dd, J ) 11.4, 4.4 Hz, 1H), 3.00-2.87 (m,
H), 2.74 (dd, J ) 13.9, 8.2 Hz, 1H), 2.57, (br s, 2H), 2.47 (dd,
3

6
998 J . Org. Chem., Vol. 63, No. 20, 1998
Lobben and Paquette
4
1
.05 (dd, J ) 4.0, 4.0 Hz, 1H), 3.04 (ddd, J ) 17.4, 8.6, 8.6 Hz,
H), 2.92 (br s, 1H), 2.76 (ddd, J ) 17.4, 5.4, 5.4 Hz, 1H), 2.56
Ack n ow led gm en t. Funds in support of this re-
search were generously provided by the U.S. Environ-
mental Protection Agency (Grant R82-4725-010). We
thank Dr. Kurt Loening for his assistance with nomen-
clature.
(
2
dd, J ) 14.4, 7.2 Hz, 1H), 2.46 (dd, J ) 14.3, 7.5 Hz, 1H),
.32 (br s, 1H), 2.12-2.05 (m, 2H); 13C NMR (75 MHz, CDCl
)
3
ppm 145.6, 136.9, 132.4, 132.1, 129.6, 128.5, 119.7, 118.9,
1
2
+
11.0, 73.5, 70.4, 45.4, 25.6, 24.1; HRMS (EI) m/z (M ) calcd
29.1103, obsd 229.1093.
tr a n s-5-Allyl-5,6,7,8-tetr a h yd r o-5,6-d ih yd r oxy-2-n a p h -
-1
Su p p or tin g In for m a tion Ava ila ble: Experimental pro-
cedures, characterization data, and the results of NOE studies
for 25a -e and 26a -e (6 pages). This material is contained
in libraries on microfiche, immediately follows this article in
the microfilm version of the journal, and can be ordered from
the ACS; see any current masthead page for ordering
information.
th on itr ile (24e): off-white solid; mp 97-98 °C; IR (KBr, cm
)
1
3
1
5
(
6
(
1
(
446 (br); H NMR (300 MHz, CDCl
3
) δ 7.54 (d, J ) 8.1 Hz,
H), 7.45 (d, J ) 8.2 Hz, 1H), 7.38 (s, 1H), 5.87-5.73 (m, 1H),
.22-5.10 (m, 2H), 3.97 (dd, J ) 11.5, 4.5 Hz, 1H), 3.05-2.89
m, 2H), 2.79-2.72 (m, 2H), 2.54 (br s, 1H), 2.39 (dd, J ) 13.9,
.9 Hz, 1H), 2.21-2.12 (m, 1H), 2.06-1.92 (m, 1H); 13C NMR
75 MHz, CDCl ) ppm 145.8, 136.1, 132.7, 132.2, 129.1, 127.4,
20.3, 118.8, 111.1, 74.8, 73.6, 40.2, 26.4, 25.7; HRMS (EI) m/z
3
+
M ) calcd 229.1103, obsd 229.1093.
J O980825F