Palladium/Lewis Acid Cocatalyzed Ring-Opening Reactions of Unsymmetrical Oxabenzonobornadienes with Oximes

Article abstract of DOI:10.1021/acs.joc.9b01094

The palladium/Lewis acid cocatalyzed ring-opening reaction of various C₁-substituted unsymmetrical oxabenzonorbornadienes (OBD) with oxime nucleophiles was investigated. The effects of various C₁ substituents were explored. Moderate to excellent yields and excellent regioselectivities were obtained for electron-withdrawing groups. The presence of electron-donating alkyl groups leads to isomerization of the corresponding OBD to afford the substituted naphthol derivatives. Additionally, a mechanism for the formation of C₂ regioisomeric ring-opened products has been proposed.

Full text of DOI:10.1021/acs.joc.9b01094

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Note
Palladium/Lewis Acid Co-Catalyzed Ring-Opening Reactions
of Unsymmetrical Oxabenzonobornadienes with Oximes
Jarvis Hill, and William Tam
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01094 • Publication Date (Web): 04 Jun 2019
Downloaded from http://pubs.acs.org on June 4, 2019
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Palladium/Lewis Acid Co-Catalyzed Ring-Opening Reactions of Unsymmetrical
Oxabenzonobornadienes with Oximes
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Jarvis Hill and William Tam*
Department of Chemistry, University of Guelph, Guelph Ontario, Canada N1G
2W1
E-mail: wtam@uoguelph.ca
Received Date (will be automatically inserted after manuscript is accepted)
ABSTRACT: The palladium/Lewis acid co-catalyzed ring-opening reaction of
various C1-substituted unsymmetrical oxabenzonorbornadienes (OBD) with
oxime nucleophiles was investigated. The effects of various C1 substituents were
explored. Moderate to excellent yields and excellent regioselectivities were
obtained for electron-withdrawing groups. The presence of electron-donating
alkyl groups lead to isomerization of the corresponding OBD to afford the
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substituted naphthol derivatives. Additionally, a mechanism for the formation of
C2 regioisomeric ring-opened products has been proposed.
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Oxabicyclic alkenes have proven to be valuable synthetic precursors for the
preparation of complex polycyclic and acyclic systems.1a-c Transition metal-
catalyzed ring-opening reactions of oxabicyclic alkenes have been extensively
investigated by Lautens, Cheng and others as well as our group on account of
their ability to generate multiple stereocenters in a single step (Scheme 1).2 Of
particular interest is the nucleophilic ring-opening reaction of oxabicyclic alkenes
as many of these products are synthetic precursors to bioactive molecules
(Scheme 1).1a The nucleophilic ring-opening reaction can provide either trans- or
cis- stereochemistry of the nucleophile to the adjacent hydroxyl group depending
on the metal catalyst and nucleophile employed.2e-f Trans- stereoisomeric ring
opened products (1a) can be obtained utilizing rhodium catalysts which assist in
nucleophilic addition (Scheme 1).2f Conversely, cis- sterioisomeric ring opened
products (1g) can be obtained utilizing a palladium catalyst (Scheme 1).2e
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Notably, in 2003, Lautens et al. employed an enantioselective reductive ring
opening reaction to obtain enantiopure 1,2-dihydronapth-1-ol, which was then
used in the synthesis of sertraline, a potent antidepressant (Scheme 1).1a, 2d
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Nu
1a
OH
[Rh(COD)Cl]2
PPF-PtBu2
Nu
O
R1
R2
ref. 2f
Cp*Ru(COD)Cl
OH
R
R2
R1
R2Zn
Pd(tol-BINAP)Cl2
1b
ref. 2a
O
ref. 2e
1g
Ni(COD)2
(R)-BINAP
DIBAL-H
Cp*Ru(COD)Cl
neutral alumina
1
NHMe
OH
ref. 2b
9-Steps
[RhCl(COD)]2
AgBF4
O
ref. 2c
(R)-BINAP
ref. 2d
1e
1c
H
H
Cl
O
Cl
O
H
H
1d
1f
Sertraline
Scheme 1. Previously reported ring-opening methodology on oxabicyclic
alkenes.
Several nucleophiles have been investigated in the ring opening reactions of
oxabicylic alkenes including various alcohols3, thiols2f, organoboronic acids4,
amines5, and carboxylates6. However, until recently there were no reported
examples of ring-opening reactions utilizing an oxime nucleophile.7 Oximes have
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become a valuable tool in organic chemistry as a result of their role in the popular
Beckmann reaction.8 Furthermore, oximes have recently attracted attention as
key structural motifs present in various antifungal agents.9 In early 2019, Fan et
al. reported the first ring opening reaction of aza/oxabicyclic alkenes (2) with
oxime nucleophiles (3) utilizing an electron poor (R)-DIFLUORPHOS ligand and
a palladium/Lewis acid co-catalyst (Scheme 2).7 The group was able to obtain
both excellent yields and enantioselectivity (4), however, only symmetrical
oxabicyclic alkenes (2) were studied (Scheme 2).
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OH
5 mmol% Pd(OAc)2
O
R
HO
R
R
O
6 mmol% (R)-DIFLUORPHOS
N
N
Ph
R
Ph
10 mmol% Zn(OTf)2, DCE, 80ºC
4 Å MS
2
3
4
64-94% yield
96-98% ee
Scheme 2. Previously reported ring-opening methodology with oxime
nucleophiles.
Substituting the C1 position of an oxabicyclic alkene renders the compound
asymmetric and thus introduces several new steric and electronic factors in the
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transition metal catalyzed ring-opening reactions. Interestingly, Lautens and
Fagnou10 obtained a single regioisomer in the rhodium catalyzed ring-opening
reaction with alcohol nucleophiles (attack on C3) (Scheme 5). Previous work by
our group11 has further demonstrated C3 regioselectivity in the palladium-
catalyzed ring opening reaction with aryl iodide nucleophiles (Scheme 5). Based
upon these findings, we set out to determine the effect of C1 substitution on
controlling regioselectivity in the palladium/Lewis acid co-catalyzed ring-opening
reaction with oxime nucleophiles (6) on unsymmetrical oxabenzonorbornadienes
(5) (OBDs) (Scheme 3).
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OH
10 mmol% Pd(OAc)2
12 mmol% (±)-BINAP
O
HO
4
O
N
3
N
R’
or
R'
N
2
R’
1
O
R
10 mmol% Zn(OTf)2, DCE, 90ºC
4 Å MS
HO R
R
C-3
5
6
C-2
7
8
Scheme 3. Potential regioisomers formed through the ring-opening reaction of
an unsymmetrical OBD.
The investigation began with methyl-substituted OBD, which afforded only
isomerized naphthol product (9) in excellent yield (95%) (Table 1, entry 1). A
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series of experiments were performed in hopes of preventing the isomerization,
including removal of the Lewis acid. However, removal of the Lewis acid resulted
only in isolation of starting material after prolonged reaction conditions. The
isomerized naphthol product (9) was also obtained for ethyl and t-butyl
substituted OBD in 90 and 91% yields, respectively (Table 1, entries 2-3). Our
group2b and many others12a-b have reported similar OBD isomerizations utilizing
similar transition metal or Lewis acid catalyzed systems. In these studies, the
electronic nature of the C1 substituent played a key role in whether or not ring-
opened products were obtained. The ring-opened product (7) could be obtained
only if the electronics of the R group at C1 were reversed through substitution
with an electron-withdrawing group rather than the electron donating alkyl group.
Moderate to good yields (64-75%) of ring-opened product (7) were obtained for
ketone, and ester substituted OBDs (Table 1, entries 4-6). Further, the product
(7) obtained was exclusively the C2 regioisomer, rather than the previously
reported C3 isomer investigated by Lautens and Fagnou10 as well as our group11
(Table 1, entries 4-6). The relative stereochemistry of the ring-opened product (7)
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was confirmed by various NMR experiments. Following these results, we then
chose the ketone substituted OBD (5e) to explore the scope with various oxime
nucleophiles (Table 1, entries 7-12). Excellent yields were obtained for o, m, p-
OMe-C6H4 substituted oxime derivatives, ranging from 85-91% yields (Table 1,
entries 7-9), whereas, poor yields were obtained for o, m, p-NO2-C6H4 ranging
from 46-49%, (Table 1, entries 10-12). The regioselective C2 addition was also
retained in all cases when utilizing the various substituted oxime nucleophiles
(Table 1, entries 7-12).
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Table 1. Ring Opening Reactions of Oxabenzonorbornadienes.
OH
OH
10 mmol% Pd(OAc)2
12 mmol% (+/-)-BINAP
O
HO
O
4
N
3
N
R’
N
R'
2
R’
O
10 mmol% Zn(OTf)2, DCE, 90ºC
4 Å MS
1
R
HO
C-2
7d-l
R
R
R
5a-e
6
C-3
9a-c
8
entry
OBD
5a
R
Me
R’
7 (%)a
8 (%)a
9 (%)a
1
2
3
4
5
Ph
Ph
Ph
Ph
Ph
0
0
0
0
0
0
0
95
90
91
0
5b
Et
tBu
5c
0
5d
COOMe
C(O)Me
74
75
5e
0
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5f
CH2OC(O)-p-
Ph
64
0
0
0
0
0
0
0
0
NO2-C6H4
C(O)Me
5e
5e
5e
p-OMe-
C6H4
91
87
85
C(O)Me
C(O)Me
m-OMe-
C6H4
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o-OMe-
C6H4
10
11
5e
5e
C(O)Me
C(O)Me
p-NO2-C6H4
m-NO2-
C6H4
49
46
0
0
0
0
12
5e
C(O)Me
o-NO2-C6H4
47
0
0
a Isolated yields after column chromatography.
A potential mechanism for the reaction can be proposed based on the relative
stereochemistry of the observed products (Scheme 4). Following the formation of
the active palladium (II) species, the palladium coordinates to the exo- face (A’),
after which, nucleophilic displacement of the acetate by the oxime nucleophile
and proton transfer leads to intermediate B’. Cis-[1,2]-migration across the exo-
face of the alkene affords the oxime derivative on the C2 position and the
palladium on C3 (C’). It is likely that substituting C1 with an electron-withdrawing
group imposes enhanced electrophilicity on the C2 site, resulting in delivery of the
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oxime nucleophile to the more electron deficient carbon (Scheme 4). Finally, β-
oxygen elimination affords the ring-opened product and regenerates the active
palladium after protonation of the oxygen bridgehead (Scheme 4). Through a
series of experiments the presence of the Zn(OTf)2 was found to be paramount
for the reactions progression. Thus, we postulate that the Lewis acid plays a
dual role, wherein it aids in the addition of the palladium across the alkene and
activates the bridgehead oxygen for the final β-oxygen elimination step.
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Pd(OAc)2
R'
(±)-BINAP
O
N
O
[Pd]*
R
HO
R
5d-f
R = EWG
Zn2+
AcO
O
O
4
Pd
3
OAc
OH
Pd OAc
O
2
1
N
R'
R
R
A’
Zn2+
C’
OAc
N
+
O
N
Pd
-
O
R’
-
+
B’
6
R
R'
Scheme 4. Potential mechanism for ring opened products.
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We have examined the substituent effects at the C1 position of various
OBD derivatives in the palladium catalyzed ring opening reaction. Throughout
these examples, it is shown that the ring-opened product obtained is exclusively
the C2 regioisomer (Table 1, entries 4-12). In addition to this, we were able to
show that the ring-opened product could only be obtained if the C1 position was
substituted with an electron-withdrawing group (Table 1, entries 4-6).
Interestingly, the single regioisomer we obtained is the opposite regioisomer (7)
obtained in previous work by Lautens and Fagnou10 as well as our group11
(Scheme 5). Thus, we have demonstrated a highly efficient method in
generating the previously elusive C2 regioisomer with an oxime nucleophile
utilizing palladium catalysis.
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OMe
OH
R
OMe
I
PdCl2(PPh3)2
Zn
This Work:
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Tam, 2014
R = EDG
C-3 Only
O
Pd(OAc)2
(+/-)-BINAP
4
3
N
R'
2
1
O
OH
R
Zn(OTf)2
R'
N
HO R
5
7
[Rh(CO)2Cl]2
TFE:MeOH (1:1)
R = EWG
C-2 Only
OH
Lautens, 2004
OMe
R
11
R = EDG
C-3 Only
Scheme 5. Previous studies on the regioselectivity of ring opening reactions with
oxabenzonobornadiene.
In conclusion, we have reported the first regioselective study into the
palladium/Lewis acid co-catalyzed ring opening reactions with oxime
nucleophiles on unsymmetrical OBDs. It was demonstrated that the reaction is
highly regioselective for the C2 position on unsymmetrical OBDs, with no C3
regioisomers formed in all cases (Table 1, entries 4-12). Further, we have also
demonstrated the requirement of electron-withdrawing groups in the
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palladium/Lewis acid co-catalyzed system, whereby substitution of the C1
position for slightly electron donating alkyl groups leads entirely to the isomerized
naphthol derivatives (Table 1, entries 1-3).
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Experimental Section
General Information: All reactions carried out in an atmosphere of dry argon. 1H
13
NMR spectra were recorded on 600 or 400 MHz in CDCl3, C{H}- NMR spectra
were recorded on 150 or 100 MHz in CDCl3. Chemical shifts for 1H NMR spectra
are reported in parts per million (ppm) with the solvent resonance as the internal
standard (chloroform:  7.26). Chemical shifts for 13C NMR spectra are reported
in parts per million with the solvent as the internal standard (chloroform:  77.16).
1H NMR spectra were recorded on 600 or 400 MHz in CDCl3, 13C{1H} proton-
decoupled carbon NMR spectra were recorded on 150 or 100 MHz in CDCl3.
Multiplicities are given as s (singlet), d (doublet), t (triplet), dd (doublet of
doublets), td (triplet of doublets), or m (multiplet). IR spectra were obtained on
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thin films on NaCl disks using a Bomem MB-100 FTIR or Nicolet-380 FTIR
spectrophotometer. Analytical thin-layer chromatography was performed on
Merck precoated silica gel 60 F254 plates. HRMS samples were ionized by
chemical ionization (CI), electron impact (EI) or electrospray ionization (ESI) as
specified, and detection of the ions was performed by time of flight (TOF). C1-
Substituted oxabenzonorbornadienes 5a-e were prepared according to known
literature procedures.3,13,14
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General Procedure for the Pd-Lewis Acid Co-Catalyzed Ring Opening Reaction
(Table 1, Entry 1): Pd(OAc)2 (4.5 mg, 0.02 mmol, 10 mol %) was weighed into an
oven dried screw-cap vial. The vial was purged with nitrogen and was taken into
inert atmosphere Drybox where (±)-BINAP (14.9 mg, 0.024 mmol) dissolved in 1
mL of DCE was added. The mixture was stirred for 30 min, after which, Zn(OTf)2
(7.3 mg, 0.02 mmol) was added in 0.4 mL of DCE. This solution was then stirred
for an additional 10 min, then 4 Å MS (0.5 mmol) were added along with the
oxabenzonorbornadiene (5a) (37 mg, 0.2 mmol) dissolved in 0.3 mL of DCE.
This solution was stirred for another 10 min and the oxime (99 mg, 0.6 mmol)
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was then added in another 0.3 mL of DCE. The entire reaction mixture was then
exported from the Drybox and stirred at 90°C (heating mantle) for 36 h. The
crude product was purified by flash chromatography to yield the corresponding
ring opened product (Ethyl acetate: hexanes mixture).
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Oxabenzonorbornadiene
5f:
C1-Substituted
hydroxymethyloxabenzonorbornadiene3 (200 mg, 1.148 mmol) was added into a
N2 purged RBF. p-NO2-Benzoylchloride (312 mg, 1.722 mmol) was then added
dilute in 1 mL of CHCl3. To this solution was then added pyridine (0.3 mL, 3.444
mmol) and the mixture was stirred for 1.5 h under ambient temperature. The
crude product was then co-concentrated with toluene (5 mL, 3×) and purified by
column chromatography to give oxabenzonorbornadiene 1a (152.7 mg, 0.5175
1
mmol, 45%) as a white solid (m.p 119-120°C). Rf 0.6 (EtOAc:pentanes 2:1); H
NMR (CDCl3, 400 MHZ)  8.24 (m, 4H), 7.28 (m, 1H), 7.23 (m, 1H), 7.13 (dd, 1H,
J= 1.8 , 5.5 Hz), 7.01 (m, 2H), 6.92 (d, 1H, J= 5.5 Hz), 5.77 (d, 1H, J= 1.8 Hz),
5.30 (d, 1H, J= 12.6 Hz), 5.15 (d, 1H, J= 12.6 Hz); 13C{1H} NMR (CDCl3, 100
MHz)  164.7, 150.8, 150.1, 147.6, 145.3, 141.9, 135.1, 131.1 (2C), 125.6, 125.3,
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126.7 (2C), 120.6, 119.4, 91.1, 82.5, 62.7; IR (CH2Cl2, NaCl) 3499 (m), 3060 (w),
2951 (w), 1734 (s), 1255 (s), 937 (m), 758 (m) cm-1; HRMS (HRESI) calcd for
C18H13NO5Na [M+Na]+ m/z 346.0691, found 346.0689.
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4-Methylnapthalenol 9a (Table 1, entry 1): The crude product was purified by
column chromatography to give the isomerized product 9a (30.1 mg, 0.190
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mmol, 95%) as a pale yellow oil: Rf 0.6 (EtOAc:hexanes 2.5:7.5); H NMR
(CDCl3, 400 MHz)  8.26 (dd, 1H, J= 1.4, 7.4 Hz), 7.98 (dd, 1H, J= 1.6, 7.9 Hz),
7.61-7.52 (m, 2H), 7.16 (dd, 1H, J= 0.8, 7.6 Hz), 6.72 (d, 1H, J= 7.6 Hz), 5.25 (s,
13
1H), 2.65 (s, 3H); C{1H} NMR (CDCl3, 100 MHz)  149.9, 133.6, 126.8, 126.4,
126.2, 125.1, 124.6, 124.3, 122.1, 108.3, 18.9. Spectral data are in accord with
those reported in the literature.15
4-Ethylnapthalenol 9b (Table 1, entry 2): The crude product was purified by
column chromatography to give the isomerized product 9b (31.0 mg, 0.179
1
mmol, 90%) as an orange oil: Rf 0.6 (EtOAc:hexanes 2.5:7.5); H NMR (CDCl3,
400 MHz)  8.23 (m, 1H), 8.02 (dd, 1H, J= 1.2, 7.6 Hz), 7.56-7.48 (m, 2H), 7.16
(d, 1H, J= 7.6 Hz), 6.75 (d, 1H, J= 7.6 Hz), 5.13 (s, 1H), 3.04 (q, 2H, J= 7.2 Hz),
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1.36 (t, 3H, J= 7.5 Hz); 13C{1H} NMR (CDCl3, 100 MHz)  149.8, 132.9, 132.7,
126.2, 124.8, 124.7, 124.5, 123.8, 122.2, 108.2, 25.4, 15.2; IR (CH2Cl2, NaCl)
3335 (w), 2966 (m), 2929 (m), 2874 (w), 1658 (m), 1624 (w), 1598 (m), 1456 (m),
1380 (m), 1300 (m), 1274 (m), 1148 (w), 1054 (w), 763 (s); HRMS (HREI) calcd
for C12H12O [M+] m/z 172.0888, found 172.0880.
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4-Tertbutylnapthalenol 9c (Table 1, entry 3): The crude product was purified by
column chromatography to give isomerized product 9c (36.1 mg, 0.180 mmol,
91%) as a purple oil: Rf 0.6 (EtOAc:hexanes 2.5:7.5); 1H NMR (CDCl3, 400 MHz)
 8.44 (dd, 1H, J= 1.2, 7.9 Hz), 8.30 (dd, 1H, J= 1.4, 8.1 Hz), 7.53-7.46 (m, 2H),
7.32 (d, 1H, J= 8.0 Hz), 6.73 (d, 1H, J= 8.0 Hz), 5.27 (s, 1H), 1.60 (s, 9H);
13C{1H} NMR (CDCl3, 100 MHz)  150.0, 138.7, 132.6, 126.8, 125.7, 126.1,
124.1, 123.0, 122.7, 107.5, 35.5, 31.9 (3C); IR (CH2Cl2, NaCl) 3378 (m), 2958
(m), 1598 (m), 823 (m), 763 (s) cm-1; HRMS (HREI) calcd for C14H16O [M+] m/z
200.1201, found 200.1201.
(E)-BenzaldehydeO-((1R,2S)-1-hydroxy-1-methoxycarbonyl-1,2-
dihydronapthalen-2-yl)oxime 7d (Table 1, entry 4): The crude product was
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purified by column chromatography to give the ring opened product 7d (47.8 mg,
0.148 mmol, 74%) as a clear oil: Rf 0.3 (EtOAc:hexanes 2.5:7.5); 1H NMR
(CDCl3, 400 MHz)  8.21 (s, 1H), 7.55 (m, 2H), 7.39 (m, 3H), 7.33 (td, 1H, J= 1.3,
7.5 Hz), 7.25 (td, 1H, J= 1.4, 7.5 Hz), 7.19 (d, 1H, J= 7.4 Hz), 7.12 (d, 1H, J= 7.6
Hz), 6.59 (dd, 1H, J= 2.6, 9.9 Hz), 6.03 (dd, 1H, J= 2.4, 9.9 Hz), 5.64 (t, 1H, J=
2.5 Hz), 3.90 (s, 3H), 3.71 (s, 1H); 13C{1H} NMR (CDCl3, 100 MHz)  175.2,
150.6, 133.9, 132.5, 131.7, 130.4, 129.6, 128.9 (2C), 128.5, 128.1, 127.5, 127.4
(2C), 126.9, 126.1, 82.3, 77.8, 53.3; IR (CH2Cl2, NaCl) 3504 (w), 3059 (w), 2951
(w), 1736 (s), 1255 (s), 937 (m), 758 (m) cm-1. HRMS (HRESI) calcd for
C19H18NO4 [M+H]+ m/z 324.1236, found 324.1234.
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(E)-BenzaldehydeO-((1R,2S)-1-hydroxy-1-methylcarbonyl-1,2-dihydronapthalen-
2-yl)oxime 7e (Table 1, entry 5): The crude product was purified by column
chromatography to give the ring opened product 7e (45.9 mg, 0.149 mmol, 75%)
as an orange oil. This experiment was repeated in a larger scale and similar
yield of 7e was obtained (554.3 mg, 1.799 mmol, 72%): Rf 0.4 (EtOAc:hexanes
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2.5:7.5); H NMR (CDCl3, 400 MHz)  8.14 (s, 1H), 7.49 (m, 2H), 7.38 (m, 3H),
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7.33 (t, 1H, J= 4.9 Hz), 7.24 (m, 1H), 7.20 (d, 1H, J= 4.9 Hz), 7.04 (d, 1H, J= 5.0
Hz), 6.62 (dd, 1H, J= 1.5, 6.5 Hz), 6.09 (dd, 1H, J= 1.8, 6.5 Hz), 5.54 (t, 1H, J=
1.7 Hz), 4.27 (s, 1H), 2.49 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz)  209.3,
150.3, 133.9, 132.9, 131.7, 130.4, 129.5, 128.9 (2C), 128.7, 128.5, 127.9, 127.4
(2C), 126.7, 126.2, 81.7, 80.7, 26.1; IR (CH2Cl2, NaCl) 3438 (w), 3026 (w), 2925
(w), 1712 (s), 1533 (m), 942 (m), 757 (s), 693 (m) cm-1; HRMS (HRESI) calcd for
C19H18NO3 [M+H]+ m/z 308.1287, found 308.1287.
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(E)-BenzaldehydeO-((1R,2S)-1-hydroxy-1-methanol-1-(4-nitrobenzoate)-1,2-
dihydronapthalen-2-yl)oxime 7f (Table 1, entry 6): The crude product was purified
by column chromatography to give the ring opened product 7f (56.8 mg, 0.128
mmol, 64%) as a yellow oil: Rf 0.4 (EtOAc:hexanes 2.5:7.5); 1H NMR (CDCl3, 400
MHz)  8.34-8.25 (m, 4H), 8.09 (s, 1H), 7.81 (dd, 1H, J= 1.2, 7.4 Hz), 7.48 (m,
2H), 7.41-7.33 (m, 5H), 7.21 (dd, 1H, J= 1.2, 7.2 Hz), 6.75 (d, 1H, J= 9.6 Hz),
6.29 (m, 1H), 5.00 (d, 1H, J= 5.8 Hz), 4.56 (d, 1H, J= 11.6 Hz), 4.38 (dd, 1H, J=
13
1.4, 11.6 Hz), 3.61 (d, 1H, J= 1.2 Hz); C{1H} NMR (CDCl3, 100 MHz)  164.5,
150.8, 150.7, 136.9, 135.5, 132.2, 131.9, 131.4, 131.0 (2C), 130.6, 129.1, 128.9
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(2C), 128.6, 127.5, 127.3 (2C), 126.1, 123.7 (2C), 123.6, 76.9, 75.1, 69.1; IR
(CH2Cl2, NaCl) 3552 (w), 3055 (w), 2952 (w), 1726 (s), 1527 (s), 1271 (s), 948
(m), 718 (m) cm-1; HRMS (HRESI) calcd for C25H21N2O6 [M+H]+ m/z 445.1400,
found 445.1400.
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(E)-4-MethoxybenzaldehydeO-((1R,2S)-1-hydroxy-1-methylcarbonyl-1,2-
dihydronapthalen-2-yl)oxime 7g (Table 1, entry 7): The crude product was
purified by column chromatography to give the ring opened product 7g (61.6 mg,
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0.183 mmol, 91%) as a yellow oil: Rf 0.3 (EtOAc:hexanes 2.5:7.5); H NMR
(CDCl3, 400 MHz)  8.09 (s, 1H), 7.43 (d, 2H, J= 8.8 Hz), 7.33 (td, 1H, J= 1.2, 7.5
Hz), 7.24-7.18 (m, 2H), 7.04 (d, 1H, J= 7.6 Hz), 6.90 (d, 2H, J= 8.8 Hz), 6.61 (dd,
1H, J= 2.3, 9.8), 6.08 (dd, 1H, J= 2.7, 9.8 Hz), 5.51 (t, 1H, J= 2.5 Hz), 4.29 (s,
1H), 3.81 (s, 3H), 2.48 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz)  209.1, 161.4,
149.9, 134.0, 133.0, 129.5, 128.9 (2C), 128.7, 128.4, 127.8, 126.7, 126.3, 124.3,
114.4 (2C), 81.8, 80.6, 55.5, 26.2; IR (CH2Cl2, NaCl) 3457 (w), 3002 (w), 2934
(w), 1712 (s), 1606 (s), 1513 (s), 1252 (s), 938 (m) cm-1; HRMS (HRESI) calcd
for C20H20NO4 [M+H]+ m/z 338.1392, found 338.1388.
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(E)-3-MethoxybenzaldehydeO-((1R,2S)-1-hydroxy-1-methylcarbonyl-1,2-
dihydronapthalen-2-yl)oxime 7h (Table 1, entry 8): The crude product was
purified by column chromatography to give the ring opened product 7g (58.6 mg,
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0.174 mmol, 87%) as an orange oil: Rf 0.4 (EtOAc:hexanes 2.5:7.5) H NMR
(CDCl3, 400 MHz)  8.11 (s, 1H), 7.34-7.19 (m, 4H), 7.04 (m , 3H), 6.94 (ddd, 1H,
J= 0.8, 2.6, 8.2 Hz), 6.62 (dd, 1H, J= 2.3, 9.84 Hz), 6.09 (dd, 1H, J= 2.76, 9.84
Hz), 5.53 (t, 1H, J= 2.5 Hz), 4.26 (s, 1H), 3.83 (s, 3H), 2.48 (s, 3H); 13C{1H} NMR
(CDCl3, 100 MHz)  208.9, 160.0, 150.1, 133.9, 132.9, 129.9, 129.5, 128.7,
128.6, 127.8, 126.7, 126.1, 120.5, 116.8, 111.4, 81.7, 80.7, 55.5, 26.1; IR
(CH2Cl2, NaCl) 3454 (m), 2933 (w), 1712 (s), 1578 (m), 1261 (m), 944 (m) cm-1;
HRMS (HRESI) calcd for C20H20NO4 [M+H]+ m/z 338.1392, found 338.1390.
(E)-2-MethoxybenzaldehydeO-((1R,2S)-1-hydroxy-1-methylcarbonyl-1,2-
dihydronapthalen-2-yl)oxime 7i (Table 1, entry 9): The crude product was purified
by column chromatography to give the ring opened product 7h (57.3 mg, 0.169
mmol, 85%) as a yellow oil: Rf 0.4 (EtOAc:hexanes 2.5:7.5); 1H NMR (CDCl3, 400
MHz)  8.54 (s, 1H), 7.59 (dd, 1H, J= 1.7, 7.7 Hz), 7.38-7.30 (m, 2H), 7.24-7.18
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(m, 2H), 7.04 (d, 1H, J= 7.6 Hz), 6.95 (t, 1H, J= 7.6 Hz), 6.89 (d, 1H, J= 8.4 Hz),
6.60 (dd, 1H, J= 2.3, 9.8 Hz), 6.09 (dd, 1H, J= 2.7, 9.8 Hz), 5.53 (t, 1H, J= 2.5
Hz), 4.32 (s, 1H), 3.83 (s, 3H), 2.47 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz) 
209.2, 157.9, 146.6, 134.0, 133.0, 131.7, 129.5, 128.6, 128.4, 127.8, 126.7 (2C),
126.4, 120.9, 120.3, 111.3, 81.9, 80.7, 55.7, 26.2; IR (CH2Cl2, NaCl) 3462 (w),
2918 (w), 2361 (w), 1711 (s), 1599 (m), 1252 (s), 938 (m), 755 (s) cm-1; HRMS
(HRESI) calcd for C20H20NO4 [M+H]+ m/z 338.1392, found 338.1394.
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(E)-4-NitrobenzaldehydeO-((1R,2S)-1-hydroxy-1-methylcarbonyl-1,2-
dihydronapthalen-2-yl)oxime 7j (Table 1, entry 10): The crude product was
purified by column chromatography to give the ring opened product 7j (34.4 mg,
0.098 mmol, 49%) as an orange liquid: Rf 0.2 (EtOAc:hexanes 2.5:7.5); 1H NMR
(CDCl3, 400 MHz)  8.23 (m, 3H), 7.64 (d, 2H, J= 8.8 Hz), 7.35 (m, 1H), 7.27 (m,
1H), 7.23 (t, 1H, J= 7.5 Hz), 7.06 (d, 1H, J= 7.5 Hz), 6.65 (dd, 1H, J= 2.1, 9.8
Hz), 6.09 (dd, 1H, J= 2.8, 9.8 Hz), 5.53 (t, 1H, J= 2.5 Hz), 4.19 (s, 1H), 2.46 (s,
13
3H); C{1H} NMR (CDCl3, 100 MHz)  208.7, 148.7, 148.0, 137.8, 133.7, 132.8,
129.7, 129.1, 128.9, 128.0, 127.9 (2C), 126.6, 125.4, 124.2 (2C), 81.6, 81.2,
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26.0; IR (CH2Cl2, NaCl) 3442 (w), 2922 (w), 2852 (w), 1712 (s), 1597 (s), 1344
(s), 951 (m) cm-1; HRMS (HRESI) calcd for C19H16N2O5Na [M+Na]+ m/z
375.0957, found 375.0956.
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(E)-3-NitrobenzaldehydeO-((1R,2S)-1-hydroxy-1-methylcarbonyl-1,2-
dihydronapthalen-2-yl)oxime 7k (Table 1, entry 11): The crude product was
purified by column chromatography to give the ring opened product 7k (32.7 mg,
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0.093 mmol, 46%) as an opaque oil: Rf 0.2 (EtOAc:hexanes 2.5:7.5); H NMR
(CDCl3, 400 MHz)  8.34 (s, 1H),  8.23 (d, 1H, J= 8.2 Hz), 8.20 (s, 1H), 7.79 (d,
1H, J= 7.7 Hz), 7.57 (t, 1H, J= 8.0 Hz), 7.35 (t, 1H, J= 6.7 hz), 7.25 (m, 2H), 7.05
(d, 1H, J= 7.5 Hz), 6.65 (dd, 1H, J= 1.9, 9.8 Hz), 6.10 (dd, 1H, J= 2.8, 9.8 Hz),
5.53 (t, 1H, J= 2.4 Hz), 4.21 (s, 1H), 2.48 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz)
 208.7, 148.7, 147.8, 133.7, 133.6, 132.8 (2C), 130.0, 129.7, 129.0, 128.9,
127.9, 126.6, 125.5, 124.7, 121.9, 81.7, 81.1, 26.0; IR (CH2Cl2, NaCl) 3453 (w),
3071 (w), 2924 (w), 1711 (s), 1530 (s), 1353 (s), 953 (m) cm-1; HRMS (HRESI)
calcd for C19H16N2O5Na [M+Na]+ m/z 375.0957, found 375.0958.
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7
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dihydronapthalen-2-yl)oxime 7l (Table 1, entry 12): The crude product was
purified by column chromatography to give the ring opened product 7l (32.7 mg,
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0.093 mmol, 47 %) as a yellow oil: Rf 0.3 (EtOAc:hexanes 2.5:7.5); H NMR
(CDCl3, 400 MHz)  8.69 (s, 1H), 8.06 (dd, 1H, J= 1.1, 8.2 Hz), 7.74 (dd, 1H, J=
1.4, 7.8 Hz), 7.65 (td, 1H, J= 0.8, 7.4 Hz), 7.55 (td, 1H, J= 1.6, 8.3 Hz), 7.34 (td,
1H, J= 1.3, 7.5 Hz), 7.27-7.20 (m, 2H), 7.05 (d, 1H, J= 7.5 Hz), 6.64 (dd, 1H, J=
2.3, 9.9 Hz), 6.10 (dd, 1H, J= 2.8, 9.8 Hz), 5.53 (t, 1H, J= 2.6 Hz), 4.19 (s, 1H),
2.45 (s, 3H); 13C{1H} NMR (CDCl3, 100 MHz)  209.1, 147.9, 146.7, 133.8, 133.7,
132.9, 130.7, 129.6, 129.0, 128.9, 128.8, 127.9, 126.9, 126.7, 125.6, 125.0, 81.7,
81.2, 26.1; IR (CH2Cl2, NaCl) 3450 (w), 3068 (w), 2922 (w), 1711 (s), 1524 (s),
1347 (s), 950 (m) cm-1; HRMS (HRESI) calcd for C19H16N2O5Na [M+Na]+ m/z
375.0957, found 375.0956.
Acknowledgements This work was supported by the Natural Sciences and
Engineering Research Council of Canada (NSERC).
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Supporting Information Available H and 13C NMR spectra all new compounds.
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This material is available free of charge via the Internet at http://pubs.acs.org.
References:
1) For reviews, see (a) Lautens, M.; Fagnou, K.; Hiebert, S. Transition Metal-
Catalyzed Enantioselective Ring-Opening Reactions of Oxabicyclic
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