Samarium(II) iodide-promoted intermolecular and intramolecular ketone- nitrile reductive coupling reactions

Article abstract of DOI:10.1055/s-2000-6220

Samarium (II) iodide, a strong one-electron transfer reducing reagent, has been successfully utilized for the intermolecular and intramolecular reductive coupling reactions of ketones with nitriles, α-Hydroxy ketones, monocyclic, fused bicyclic α-hydroxy ketones and monocyclic α-amino alcohols composed of a number of substitution patterns have been prepared in good yields at room temperature or reflux under neutral conditions. The procedure can avoid overreduction of the resulting of α-hydroxy ketones or α-amino alcohols. The crystal structures of monocyclic α-amino alcohols are reported.

Full text of DOI:10.1055/s-2000-6220

PAPER
91
Samarium(II) Iodide-Promoted Intermolecular and Intramolecular Ketone-
Nitrile Reductive Coupling Reactions
Longhu Zhou,a,b Yongmin Zhang,*a Daqing Shib
a Department of Chemistry, Zhejiang University (Campus Xixi), Hangzhou, 310028, P. R. China
Fax +86(571)8273802
b Department of Chemistry, Xuzhou Normal University, Xuzhou, 221009, P. R. China
Received 21 June 1999; revised 9 August 1999
a-Ketols are versatile synthetic intermediates and partial
structures of various biologically active compounds such
as cortisone acetates8 and adriamycin acetate.9 The meth-
ods for synthesis of a-ketols from alkenes10 and mono-ox-
Abstract: Samarium (II) iodide, a strong one-electron transfer re-
ducing reagent, has been successfully utilized for the intermolecular
and intramolecular reductive coupling reactions of ketones with ni-
triles. a-Hydroxy ketones, monocyclic, fused bicyclic a-hydroxy
ketones and monocyclic a-amino alcohols composed of a number of ygenated compounds such as enol ethers11 and enolates12
substitution patterns have been prepared in good yields at room
temperature or reflux under neutral conditions. The procedure can
have been studied extensively. a-Ketols can also be pro-
duced by ketyl-nitrile reductive coupling using one-elec-
avoid overreduction of the resulting of a-hydroxy ketones or a-ami-
tron reducing agents such as Cp2TiPh,13 Zn/TMSCl14 and
no alcohols. The crystal structures of monocyclic a-amino alcohols
15
SmI2 in addition to the electroreductive method.16 Al-
are reported.
though the reaction of other functional groups promoted
Key words: samarium diiodide, ketone-nitrile, reductive coupling,
by SmI2 have been studied, little attention has been given
cyclizations, a-ketols, a-amino alcohols, aldehydes, ketones,
to the reaction of nitriles with this agent.17 It is well known
heterocycles
that the carbonyl group can easily be reduced by SmI2.
However, the cyano group is more stable to samarium di-
iodide than the carbonyl group and could not be coupled
by this reagent.18 In our previous work, we have reported
a novel cyclodimerization of arylidenemalononitriles and
arylidenecyanoacetates, and intermolecular and intramo-
lecular reductive coupling of nitriles with nitro com-
pounds promoted by SmI2.19 Recently Molander reported
the intramolecular ketyl-nitrile coupling promoted by
SmI2 under irradiation with a 250 W floodlamp. 15 Herein,
we wish to report our results on intermolecular and in-
tramolecular ketone-nitrile reductive couplings promoted
by SmI2 in tetrahydrofuran at room temperature or under
reflux conditions.
Introduction
Applications of samarium(II) iodide to organic synthesis
have significantly grown in the last decade.1 Pioneering
work performed by Kagan with SmI2 has served to outline
the uses of this reagent in synthetic organic chemistry. Ka-
gan and co-workers’ investigations have been followed by
reports from other scientists, revealing that SmI2 is an ex-
ceedingly reliable, mild, neutral, selective and versatile
single electron transfer agent for promoting reductive re-
actions difficult to accomplish by other existing method-
ologies.
Carbonyl coupling reactions passing through a ketyl inter-
mediate constitute an important class of reactions in or-
ganic chemistry. For instance, ketone-olefin couplings,2
and intermolecular and intramolecular pinacol coupling
reactions3 have been conducted using SmI2 as the reagent.
It has been reported that ketyls can also be produced by
photochemical4 and electrochemical processes,5 low-va-
lent titanium reagent6 and other reductants.7
Intermolecular Ketone-Nitrile Cross Reductive Cou-
pling Reactions
Reaction of 1 equivalent of ketones (or aldehydes) 1 and
about 1.2 equivalents of nitriles 2 with 2.2 equivalents of
SmI2 gave a-hydroxy ketones 3 (or pinacols 4) (Scheme
1). Table 1 summarizes the results on the intermolecular
ketone-nitrile reductive couplings. When benzophenone
and aromatic nitriles were heated at reflux with SmI2 un-
Scheme 1
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92
L. Zhou et al.
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Table 1 The Intermolecular Cross Reductive Coupling of Ketones
with Nitriles
Table 2 Intermolecular Reductive Coupling of Dibenzoylmethane
with Nitriles
Entry R1
R2
Reaction
Time (h)
Yield (%)a,b
Entry
R
Reaction Time (h) Yield (%)a
3
4
1
2
Ph
4-MeC6H4
48
40
61
45
1
2
Ph
Ph
Ph
4
5
5
4
6
2.5
4
5
24
8
8
78c
75c
87c
76c
75c
83c
70c
77c
45d
–
–
–
–
–
–
–
–
–
4-ClC6H4
3-MeC6H4
4-MeC6H4
4-MeOC6H4
Ph
a Yield isolated products 7a and b.
3
Ph
4
Ph
5
Ph
6
7
4-MeC6H4
4-MeC6H4
Intramolecular Ketone-Nitrile Reductive Coupling
Reactions
4-MeC6H4
8
4-MeOC6H4 4-ClC6H4
9
Ph
H
H
Ph
–
10
11
12
4-ClC6H4
4-ClC6H4
Ph
81c
86d
44c
The intramolecular reductive coupling of the keto nitrile 8
was found to be similar to the intermolecular one. When a
solution of 1 equivalent of 8 in anhydrous THF was al-
lowed to react with 2.2 equivalents SmI2 in anhydrous
THF under the same reaction conditions, the reductive cy-
clization took place to provide a 78% yield of the a-hy-
droxy ketone 9.
–
Me
10
30c
aYields of isolated products 3a–i and 4a,b
b1 mmol of 1 and about 1.2 mmol of 2 were used
cReaction was carried out under reflux
dReaction was carried out at room temperature
der nitrogen, a-hydroxy ketones 3 were obtained in good
yields (Entries 1-8). If the reaction was carried out at
room temperature, it was slow and gave lower yields (En-
try 9). Addition of HMPA20 or LiCl21 to the reaction mix-
ture gave no evident change. On the other hand, treatment
of aromatic aldehydes and nitriles with SmI2 at room tem-
perature, even under reflux conditions did not give a-hy-
droxy ketones 3, only pinacol coupling products 4a,b
were obtained in good yields (Entries 10 and 11). Reac-
tion of acetophenone and benzonitrile with SmI2, gave a-
hydroxy ketones 3i, along with pinacol 4b (Entry 12). For
comparison, when the same reaction was carried out using
TiCl4/Zn as the reductant at reflux temperature, the cross
coupling product ketone was obtained along with an
olefin22 while a-hydroxy ketone was not found.
Scheme 3
The cis stereochemistry of 9 was determined by compari-
son of its 13C NMR spectrum with the reported data.
Hence it is reasonable to suggest that the strain of transi-
tion structure does not lead to the formation of trans-fused
bicyclo[4,3,0]system.15c, 16 The keto nitrile 10 was cy-
clized to give the a-hydroxy ketone 11 in 85% under the
same reaction conditions.
The intramolecular pinacol coupling reaction of diketones
can be promoted smoothly by SmI2.1,3 Attempts to induce
the cross coupling between nitriles and diketones were un-
successful. Ketones are far more reactive than nitriles and
intramolecular reaction could occur much easier than in-
termolecular one. An exception is the case of dibenzoyl-
methane (5). When dibenzoylmethane (5) and nitriles 6
were treated with SmI2 at reflux conditions, pyrroles 7
were formed in moderate yield (Table 2). The great steric
strain for the intramolecular cyclization of dibenzoyl-
methane is probably the reason why the coupling reaction
is driven to take an intermolecular way.
Scheme 4
Substrates 12, which possess a carbonyl group and a dicy-
ano group, can undergo intramolecular ketyl-nitrile reduc-
tive coupling reaction smoothly even if at room
temperature under nitrogen. The reductive cyclization
products 1,4-diaryl-2-amino-3-cyanocyclopent-2-ene-1-
ols 13 were obtained along with their diastereomers 14
(Scheme 5).
Table 3 summarizes the results on the intramolecular cy-
clization of g-keto nitriles. All substrates were cyclized in
good yields. The reaction is highly chemoselective; only
Scheme 2
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Samarium(II) Iodide-Promoted Intermolecular and Intramolecular Ketone-Nitrile
93
Scheme 5
two isomers were obtained. The pinacol coupling prod-
ucts of ketones were not detected. The yield of product 14
is much higher than that of 13. The chloro and alkoxyl
groups of the substrates could not be reduced under the re-
action conditions. The structures and relative configura-
tion of the products have been established using
spectroscopic data and by X-ray analysis. The X-ray dif-
fraction studies on single crystals of 13c and 14c indicate
that the products 13 (1,4-cis) and 14 (1,4-trans) are dia-
stereoisomers (Figure 1 and Figure 2).
Figure 2 ORTEP diagram of 14c
closure occurs via radical addition to the nitrile group.
Then the carbon-nitrogen double bond is transformed to
form a carbon-carbon double bond due to stabilization by
the cyano group. In the intermolecular reaction (Scheme
1) and other intramolecular reaction (Schemes 3 and 4),
however, the carbon-nitrogen double bond could not be
transferred to form a carbon-carbon double bond and in
the absence of a cyano group, a-hydroxy ketones are
formed. On the other hand, the ketyl radical (A’) from ar-
omatic aldehydes has less steric hindrance than that of
benzophenone and the pinacol coupling reaction could
proceed prior to the ketone-nitrile reaction.
Figure 1 ORTEP diagram of 13c
Though the detailed mechanism of the above reductive
coupling reaction has not been clarified yet, the formation
of monocyclic a-amino alcohols and a-hydroxy ketones
may be explained by the possible mechanism presented in
Scheme 6.
In summary, the behavior of SmI2 applied to the ketone-
nitrile reductive coupling reactions has been studied. Al-
though the cross coupling reaction of aldehyde with nitrile
did not occur, the reactions afford a variety of a-hydroxy
ketones or a-amino alcohols in good yield. Further studies
to develop other new reactions using SmI2 are now in
progress.
In the intramolecular ketone-nitrile coupling reaction
(Scheme 5), after the formation of ketyl anion (A), ring
THF was distilled from sodium/benzophenone immediately prior to
use. All reactions were performed under N2 using syringes and
Schlenk-type techniques.
Table 3 The Intramolecular Reductive Coupling of g-Keto Nitriles
Entry R1
R2
Reaction
Time (h)
Yield (%)a,b
Melting points are uncorrected. IR spectra were recorded on Perkin
Elmer 683 or FTIR-8101 spectrometers in KBr or CCl4 solution.
NMR spectra were recorded on a Bruker AC-300 (1H, 300 MHz,
13C, 75 MHz) or a JEOL PMX-60 spectrometer. J values are in
Hertz. Chemical shifts are expressed in ppm downfield from inter-
nal TMS. Mass spectra were recorded on a HP 5989A or a Finnigan
MAT GCMS spectrometer. Microanalysis were carried out on a
Carlo-Erba 1106 instrument.
13
14
1
2
3
4
5
6
7
Ph
4-ClC6H4
4-ClC6H4
3,4-OCH2OC6H3 Ph
2-ClC6H4
Ph
Ph
2
1
2
2.5
1.5
2
23
30
25
21
23
27
–
49
54
55
48
53
47
68
4-MeC6H4
Ph
Ph
4-MeC6H4
Ph
4-MeC6H4
2
a Reactions were carried out at room temperature. Yields of isolated
products 13a–f and 14a–g.
b 2.2 mmol SmI2 and 1 mmol of 1 were used.
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L. Zhou et al.
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Scheme 6
SmI2-Promoted Preparation a-Hydroxy Ketones; General Pro-
cedure
1H NMR (CCl4): d = 2.07 (3 H, s, CH3), 4.80 (1 H, s, OH), 6.75-
7.60 (14 H, m, ArH).
To Sm (331 mg, 2.2 mmol) in anhyd THF (22 mL) was added I2
(558 mg, 2.2 mmol). The resultant orange slurry was stirred vigor-
ously for 2 h at r.t. The resulting SmI2 solution had a deep blue-
green colour. A solution of ketone (or aldehyde) 1 (1 mmol) and ni-
trile 2 (1.2 mmol) in anhyd THF (3 mL) was added at r.t. under dry
N2. The mixture was then stirred at reflux. After the reaction was
complete, the mixture was quenched with dil HCl (5% HCl, 2 mL).
The solution was extracted with Et2O (3 × 40 mL) and the combined
extracts were washed with aq satd solution of Na2S2O3 (15 mL),
brine (15 mL), and dried (Na2SO4). After evaporating the solvent
under reduced pressure, the crude product was purified by prepara-
tive TLC on silica gel using EtOAc/cyclohexane (1:10) as eluent.
2-Hydroxy-2,2,-diphenyl-1-(p-tolyl)ethanone (3d)
Compound 3d was obtained from benzophenone (182 mg, 1 mmol)
and p-tolunitrile (141 mg, 1.2 mmol) as a white solid in 76% yield;
mp 56-57°C (Lit.24 mp 57-59°C).
IR (KBr): n = 3480, 1680 cm-1.
1H NMR (CCl4): d = 2.16 (3 H, s, CH3), 5.10 (1 H, s, OH), 6.86-
7.75 (14 H, m, ArH).
2-Hydroxy-1-(4-methoxyphenyl)-2,2-diphenylethanone (3e)
Compound 3e was obtained from benzophenone (182 mg, 1 mmol)
and 4-methoxybenzonitrile (160 mg, 1.2 mmol) as a white solid in
75% yield; mp 131-133°C (Lit.24 mp 132-133.5°C).
IR (KBr): n = 3410, 1675 cm-1.
1H NMR (CDCl3): d = 3.78 (3 H, s, OCH3), 5.08 (1 H, s, OH), 6.70-
7.90 (14 H, m, ArH).
2-Hydroxy-1,2,2,-triphenylethanone (3a)
Compound 3a was obtained from benzophenone (182 mg, 1 mmol)
and benzonitrile (134 mg, 1.3 mmol) as a white solid in 78% yield;
mp 85-86°C (Lit.23 mp 84°C).
IR (KBr) n = 3510, 1680 cm-1.
2-Hydroxy-1,2-diphenyl-2-(p-tolyl)ethanone (3f)
Compound 3f was obtained from 4-methylbenzophenone (196.3
mg, 1 mmol) and benzonitrile (144 mg, 1.4 mmol) as a pale yellow
oil in 83% yield (Lit.25 bp 216-219°C/2.7 Torr).
IR (neat): n = 3460, 1680 cm-1.
1H NMR (CCl4): d = 2.27 (3 H, s, CH3), 4.70 (1 H, br s, OH), 6.90-
7.70 (14 H, m, ArH).
1H NMR (CDCl3): d = 4.96 (1 H, br s, OH, exchangeable), 7.13-
7.72 (15 H, m, ArH).
2-Hydroxy-1-(4-chlorophenyl)-2,2,-diphenylethanone (3b)
Compound 3b was obtained from benzophenone (182 mg, 1 mmol)
and 4-chlorobenzonitrile (165 mg, 1.2 mmol) as a white solid in
75% yield; mp 86-88°C (Lit.24 mp 87-88°C).
IR (KBr) n = 3490, 1690 cm-1.
1H NMR (CDCl3): d = 4.55 (1 H, s, OH), 6.80-7.80 (14 H, m, ArH).
2-Hydroxy-2-phenyl-1,2-di(p-tolyl)ethanone (3g)
Compound 3g was obtained from 4-methylbenzophenone (196.3
mg, 1 mmol) and p-tolunitrile (129 mg, 1.1 mmol) as a colorless oil
in 70% yield.26
IR (neat): n = 3480, 1680 cm-1.
1H NMR (CCl4): d = 2.20 (3 H, s, CH3), 2.27 (3 H, s, CH3), 4.75 (1
H, br s, OH), 6.90-7.80 (13 H, m, ArH).
2-Hydroxy-2,2-diphenyl-1-(m-tolyl)ethanone (3c)
Compound 3c was obtained from benzophenone (182 mg, 1 mmol)
and o-tolunitrile (141 mg, 1.2 mmol) as an oil in 76% yield; bp 180-
187°C/0.2 Torr (Lit.24 mp 175 - 180°C/0.1 Torr).
IR (neat): n = 3470, 1680 cm-1.
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Samarium(II) Iodide-Promoted Intermolecular and Intramolecular Ketone-Nitrile
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1-(4-Chlorophenyl)-2-hydroxy-2-(4-methoxyphenyl)-2-phe-
nylethanone (3h)
Compound 3h was obtained from 4-methoxybenzophenone (21.3
mg, 1 mmol) and 4-chlorobenzonitrile (151 mg, 1.1 mmol) as a
white solid in 77% yield; mp 92-94°C (Lit.26 mp 93-94°C).
2-Hydroxy-2-phenylcyclopentan-1-one (11)
Compound 11 was prepared from the keto nitrile 10 according to the
general procedure for 3. Purification by preparative TLC on silica
gel using EtOAc/cyclohexane (1:4) as eluent afforded 11 as a pale
yellow oil in 85% yield.28
IR (KBr): n = 3480, 1690 cm-1.
1H NMR (CDCl3): d = 3.60 (3 H, s, OCH3), 4.23 (1 H, br s, OH),
6.50 - 7.80 (13 H, m, ArH).
IR (neat): n = 3450, 2980, 1750 cm-1.
1H NMR (CDCl3): d = 1.73-1.89 (1 H, m), 1.96-2.10 (1 H, m),
2.15-2.26 (1 H, m,), 2.38-2.50 (3 H, m), 3.19 (1 H, br s, OH),
7.24-7.35 (5 H, m, ArH).
MS (EI, 70 eV): m/z (%) = 176 (M+, 7), 148 (100), 120 (98), 105
(97), 91 (18), 77 (39), 51 (15).
2-Hydroxy-2-methyl-1,2-diphenylethanone (3i)
Compound 3i was obtained from acetophenone (120.2 mg, 1 mmol)
and benzonitrile (124 mg, 1.2 mmol) as a solid in 30% yield; mp
66-68°C (Lit.25 mp 68-69°C).
IR (KBr): n = 3470, 1690 cm-1.
SmI2-Promoted Preparation of a-Amino Alcohols
To SmI2 (331 mg, 2.2 mmol) in anhyd THF (22 mL) was added a
solution of keto nitrile 12 (1 mmol) in anhyd THF (3 mL) at r.t. un-
der N2. The mixture was then stirred at r.t. for about 2 h. After this
period, the TLC analysis of the mixture showed the reaction to be
complete. The reaction was quenched with 5 % dil HCl (2 mL). The
mixture was extracted with Et2O (3 ¥ 30 mL) and the combined ex-
tracts were washed with aq satd Na2S2O3 solution (10 mL), brine
(15 mL), and dried (Na2SO4). After evaporating the solvent under
reduced pressure, the crude product purified by preparative TLC on
silica gel using EtOAc/cyclohexane (1:2) as eluent.
1H NMR (CCl4): d = 1.43 (3 H, s, CH3), 3.40 (1 H, br s, OH), 6.90-
7.50 (9 H, m, ArH).
SmI2-Promoted Preparation of Pyrroles 7
To SmI2 (1.62 g, 4 mmol) in anhyd THF (40 mL) was added a solu-
tion of dibenzoylmethane (5; 224 mg, 1 mmol) and nitrile 6 (1.5
mmol) in anhyd THF (3 mL) at r.t. under N2. The mixture was then
stirred at reflux about 2 d. After this period, TLC analysis of the
mixture showed the reaction to be complete. The reaction was
quenched with aq 10% K2CO3 solution (10 mL). The mixture was
extracted with CH2Cl2 (3 × 30 mL) and the combined extracts were
washed with brine (15 mL), and dried (Na2SO4). After evaporating
the solvent under reduced pressure, the crude product was purified
by preparative TLC on silica gel using Et2O/petroleum (1:6) as elu-
ent.
cis-2-Amino-3-cyano-1,4-diphenylcyclopent-2-en-1-ol (13a)
Compound 13a was obtained from 12a as a white solid in 23%
yield; mp 168-170°C.
IR (KBr): n = 3440, 3320, 2200, 1670, 1610, 1500 cm-1.
1H NMR (CDCl3): d = 1.98-2.23 (2 H, dd, J = 13.2, 7.5 Hz, C5-H,
OH), 2.68-2.93 (1 H, dd, J = 13.2, 7.1 Hz, C5-H), 3.83-4.01 (1 H,
dd, J = 7.5, 7.1 Hz, C4-H), 4.65 (2 H, br s, NH2), 7.23-7.42 (10 H,
m, ArH).
2, 3, 5-Triphenylpyrrole (7a)
Compound 7a was obtained from dibenzoylmethane and benzoni-
trile in 61% yield; mp 139-140°C (Lit.27 mp 142°C).
IR (KBr): n = 3460, 1610, 1510, 1495, 1455, 1265, 1180, 1070,
MS (EI, 70 eV): m/z (%) = 276 (M+, 34), 258 (M+ - H2O, 100), 257
(61), 181 (25), 171 (9), 155 (20), 154 (23), 105 (69), 77 (75).
955, 760, 690 cm-1.
1H NMR (CDCl3): d = 6.50 (1 H, s, CH), 7.05-7.75 (15 H, m, ArH),
8.20 (1 H, s, NH).
Anal. Calcd for C18H16N2O: C, 78.24; H, 5.83; N, 10.14. Found: C,
78.50; H, 5.60; N, 9.97.
3, 5-Diphenyl-2-(p-tolyl)pyrrol (7b)
Compound 7b was obtained from dibenzoylmethane and 4-methyl-
benzonitrile in 45% yield; mp 104-105°C.
trans-2-Amino-3-cyano-1,4-diphenylcyclopent-2-en-1-ol (14a)
Compound 14a was obtained from 12a as a white solid in 49%
yield; mp 164-165°C.
IR (KBr): n = 3420, 1600, 1480, 1450, 1260, 1070, 810, 790, 760,
IR (KBr): n = 3480, 3360, 2200, 1660, 1610, 1500 cm-1.
1H NMR (CDCl3): d = 2.05-2.32 (2 H, dd, J = 14.2, 7.5, C5-H, OH),
2.58-2.85 (1 H, dd, J = 14.2, 7.3, C5-H), 4.21-4.40 (3 H, dd, J =
7.5, 7.3, C4-H, NH2), 7.26-7.50 (10 H, m, ArH).
700 cm-1.
1H NMR (CDCl3): d = 2.30 (3 H, s, CH3), 6.65 (1 H, s, CH), 7.05-
7.70 (14 H, m, ArH), 8.30 (1 H, s, NH).
MS (EI, 70 eV): m/z (%) = 309 (M+, 100), 191 (11), 146 (7), 105 (8).
MS (EI, 70 eV): m/z (%) = 276 (M+, 59), 258 (M+ - H2O, 100), 181
(24), 171 (10), 155 (22), 154 (23), 105 (66), 77 (67).
Anal. Calcd for C23H19N: C, 89.28; H, 6.10; N, 4.53. Found: C,
88.95; H, 6.10; N, 4.62.
Anal. Calcd for C18H16N2O: C, 78.24; H, 5.83; N, 10.14. Found: C,
78.47; H, 5.57; N, 9.88.
cis-6-Hydroxybicyclo[4.3.0]nonan-7-one (9)
Compound 9 was prepared from the keto nitrile 8 according to the
general procedure for 3. Purification by preparative TLC on silica
gel using EtOAc/cyclohexane (1:4) as eluent afforded 9 as a color-
less oil in 78% yield.
cis-2-Amino-4-(4-chlorophenyl)-3-cyano-1-(p-tolyl)cyclopent-
2-en-1-ol (13b)
Compound 13b was obtained from 12b as a white solid in 30%
yield; mp 187 - 189°C.
IR (neat): n = 3460, 1750 cm-1.
1H NMR (CDCl3): d = 1.13-1.30 (1 H, m), 1.40-1.83 (9 H, m),
2.05-2.47 (3 H, m,), 3.60 (1 H, br s, OH).
13C NMR (CDCl3): d = 20.60, 20.72, 20.95, 24.35, 29.37, 33.28,
40.80, 77.75, 219.80.
MS (EI, 70 eV): m/z (%) = 154 (M+, 13), 98 (100), 70 (32), 55 (32).
IR (KBr): n = 3470, 3420, 3365, 2180, 1675, 1615, 1500 cm-1.
1H NMR (CDCl3): d = 1.90 - 2.17 (1 H, dd, J = 13.0, 7.5, C5-H),
2.37 (3 H, s, CH3), 2.64-2.89 (2 H, dd, J = 13.0, 7.1, C5-H, OH),
3.77-3.95 (1 H, dd, J = 7.5, 7.1, C4-H), 4.58 (2 H, br s, NH2), 7.14-
7.40 (8 H, m, ArH).
MS (EI, 70 eV): m/z (%) = 326 ([M + 2]+, 7), 324 (M+, 21), 308
(37), 306 (M+ - H2O, 100), 289 (28), 271 (26), 256 (14), 215 (16),
205 (5), 189 (6), 188 (4), 119 (64), 91 (55).
Anal. Calcd for C9H14O2: C, 70.10; H, 9.15. Found: C, 69.87; H,
9.40.
Anal. Calcd for C19H17ClN2O: C, 70.26; H, 5.27; N, 8.62. Found: C,
70.50; H, 5.45; N, 8.36.
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trans-2-Amino-4-(4-chlorophenyl)-3-cyano-1-(p-tolyl)cyclo-
pent-2-en-1-ol (14b)
IR (KBr): n = 3500, 3370, 3260, 2200, 1660, 1610, 1490,
1450 cm-1.
Compound 14b was obtained from 12b as a white solid in 54%
yield; mp 170-172°C.
IR (KBr): n = 3490, 3390, 3250, 2190, 1660, 1605, 1500 cm-1.
1H NMR (CDCl3): d = 1.94-2.21 (1 H, dd, J = 14.2, 7.4 Hz, C5-H),
2.34 (3 H, s, CH3), 2.52-2.79 (2 H, dd, J = 14.2, 7.3 Hz, C5-H, OH),
4.41-4.32 (1 H, dd, J = 7.4, 7.3 Hz, C4-H), 4.51 (2 H, br s, NH2),
7.11-7.38 (8 H, m, ArH).
MS (EI, 70 eV): m/z (%) = 326 ([M + 2]+, 17), 324 (M+, 49), 308
(35), 306 (M+ - H2O, 99), 289 (80), 271 (55), 256 (24), 215 (10),
205 (7), 189 (8), 188 (6), 119 (100), 91 (74).
1H NMR (CDCl3): d = 2.00-2.27 (2 H, dd, J = 14.2, 7.5 Hz, C5-H,
OH), 2.54-2.81 (1 H, dd, J = 14.2, 7.3 Hz, C5-H), 4.13-4.32 (1 H,
dd, J = 7.5, 7.3 Hz, C4-H), 4.41 (2 H, br s, NH2), 5.94 (2 H, s,
OCH2O), 6.75 (3 H, s, ArH), 7.30-7.50 (5 H, m, ArH).
MS (EI, 70 eV): m/z (%) = 320 (M+, 100), 302 (M+ - H2O, 38), 105
(28), 77 (16).
Anal. Calcd for C19H16N2O3: C, 71.24; H, 5.04; N, 8.74. Found: C,
71.61; H, 5.35; N, 8.61.
cis-2-Amino-3-cyano-4-(2-chlorophenyl)-1-phenylcyclopent-2-
en-1-ol (13e)
Anal. Calcd for C19H17ClN2O: C, 70.26; H, 5.27; N, 8.62. Found: C,
70.04; H, 5.13; N, 8.81.
Compound 13e was obtained from 12e as a white solid in 23%
yield; mp 171-172°C.
cis-2-Amino-4-(4-chlorophenyl)-3-cyano-1-phenylcyclopent-2-
en-1-ol (13c)
Compound 13c was obtained from 12c as a white solid in 25%
yield; mp 178-180°C.
IR (KBr): n = 3430, 3370, 3250, 2180, 1675, 1605, 1455 cm-1.
1H NMR (CDCl3): d = 1.87-2.12 (2 H, dd, J = 13.5, 6.4 Hz, C5-H,
OH), 2.82-3.02 (1 H, dd, J = 13.5, 7.6 Hz, C5-H), 4.38-4.47 (1 H,
dd, J = 7.6, 6.4 Hz, C4-H), 4.66 (2 H, br s, NH2), 7.19-7.49 (9 H, m,
ArH).
IR (KBr): n = 3490, 3420, 3360, 2180, 1680, 1625, 1500 cm-1.
1H NMR (CDCl3): d = 1.93-2.19 (2 H, dd, J = 13.0, 7.5 Hz, C5-H,
OH), 2.66-2.91 (1 H, dd, J = 13.0, 7.0 Hz, C5-H), 3.79-3.97 (1 H,
dd, J = 7.5, 7.0 Hz, C4-H), 4.70 (2 H, br s, NH2), 7.25-7.50 (9 H, m,
ArH).
MS (EI, 70 eV): m/z (%) = 312 ([M + 2]+, 10), 310 (M+, 29), 294
(36), 292 (M+ - H2O, 100), 275 (53), 257 (41), 215 (10), 205 (8),
189 (7), 105 (62), 77 (48).
MS (EI, 70 eV): m/z (%) = 312 ([M + 2]+, 17), 310 (M+, 48), 294
(28), 292 (M+ - H2O, 74), 275 (4), 257 (31), 215 (7), 205 (5), 189
(5), 105 (64), 77 (100).
Anal. Calcd for C18H15ClN2O: C, 69.57; H, 4.87; N, 9.01. Found: C,
69.83; H, 4.65; N, 9.18.
trans-2-Amino-3-cyano-4-(2-chlorophenyl)-1-phenylcyclopent-
2-en-1-ol (14e)
Anal. Calcd for C18H15ClN2O: C, 69.57; H, 4.87; N, 9.01. Found: C,
69.82; H, 4.99; N, 8.87.
Compound 14e was obtained from 12e as a white solid in 53%
yield; mp 183-185°C.
trans-2-Amino-4-(4-chlorophenyl)-3-cyano-1-phenylcyclopent-
2-en-1-ol (14c)
Compound 14c was obtained from 12c as a white solid in 55%
yield; mp 191-193°C.
IR (KBr): n = 3460, 3370, 3250, 2190, 1660, 1610, 1460 cm-1.
1H NMR (CDCl3): d = 1.92-2.19 (1 H, dd, J = 14.3, 6.8 Hz, C5-H),
2.73-3.00 (2 H, dd, J = 14.3, 7.7 Hz, C5-H, OH), 4.57 (2 H, br s,
NH2), 4.67-4.83 (1 H, dd, J = 7.7, 6.8 Hz, C4-H), 7.15-7.36 (9 H,
m, ArH).
IR (KBr): n = 3500, 3390, 2200, 1660, 1605, 1500 cm-1.
1H NMR (CDCl3): d = 2.00-2.27 (2 H, dd, J = 14.1, 7.5 Hz, C5-H,
OH),2.57-2.84 (1 H, dd, J = 14.1, 7.3 Hz, C5-H), 4.18-4.37 (3 H,
dd, J = 7.5, 7.0 Hz, C4-H, NH2), 7.13-7.41 (9 H, m, ArH).
MS (EI, 70 eV): m/z (%) = 312 ([M + 2]+, 21), 310 (M+, 47), 294
(34), 292 (M+ - H2O, 89), 275 (5), 257 (12), 215 (5), 205 (4), 189
(3), 105 (68), 77 (100).
MS (EI, 70 eV): m/z (%) = 312 ([M + 2]+, 14), 324 (M+, 39), 294
(33), 292 (M+ - H2O, 95), 275 (100), 257 (48), 215 (6), 205 (7), 189
(7), 105 (85), 77 (58).
Anal. Calcd for C18H15ClN2O: C, 69.57; H, 4.87; N, 9.01. Found: C,
69.79; H, 4.63; N, 9.25.
cis-2-Amino-3-cyano-4-phenyl-1-(p-tolyl)cyclopent-2-en-1-ol
Anal. Calcd for C18H15ClN2O: C, 69.57; H, 4.87; N, 9.01. Found: C,
69.75; H, 4.65; N, 9.17.
(13f)
Compound 13f was obtained from 12f as a white solid in 27% yield;
mp 196-98°C.
IR (KBr): n = 3420, 3370, 3250, 2190, 1675, 1640, 1610 cm-1.
cis-2-Amino-3-cyano-4-(3, 4-methylenedioxyphenyl)-1-phenyl-
cyclopent-2-en-1-ol (13d)
Compound 13d was obtained from 12d as pale yellow crystals in
21% yield; mp 164 - 166°C.
1H NMR (CDCl3): d = 1.96-2.00 (1 H, dd, J = 13.4, 7.3 Hz, C5-H),
2.38 (3 H, s, CH3), 2.65-2.88 (2 H, dd, J = 13.4, 7.3 Hz, C5-H, OH),
3.80-3.98 (1 H, dd, J = 7.3, 7.3 Hz, C4-H), 4.65 (2 H, br s, NH2),
7.23-7.45 (9 H, m, ArH).
IR (KBr): n = 3470, 3390, 3250, 2200, 1660, 1610, 1510,
1455 cm-1.
1H NMR (CDCl3): d = 1.93-2.16 (2 H, dd, J = 13.0, 7.5 Hz, C5-H,
OH), 2.64-2.91 (1 H, dd, J = 13.0, 7.0 Hz, C5-H), 3.75-3.94 (1 H,
dd, J = 7.5, 7.0 Hz, C4-H), 4.68 (2 H, br s, NH2), 5.94 (2 H, s,
OCH2O), 6.72-6.78 (3 H, m, ArH), 7.35-7.61 (5 H, m, ArH).
MS (EI, 70 eV): m/z (%) = 320 (M+, 100), 302 (M+ - H2O, 47), 105
(33), 77 (23).
MS (EI, 70 eV): m/z (%) = 290 (M+, 38), 272 (M+ - H2O, 100), 257
(22), 198 (21), 181 (14), 171 (6), 155 (10), 154 (7), 119 (42), 91
(34).
Anal. Calcd for C19H18N2O: C, 78.60; H, 6.25; N, 9.65. Found: C,
78.78; H, 6.12; N, 9.82.
trans-2-Amino-3-cyano-4-phenyl-1-(p-tolyl)cyclopent-2-en-1-ol
Anal. Calcd for C19H16N2O3: C, 71.24; H, 5.04, N, 8.74. Found: C,
71.51; H, 5.16; N, 8.61.
(14f)
Compound 14f was obtained from 12f as a white solid in 47% yield;
mp 165-166.
IR (KBr): n = 3500, 3400, 2200, 1650, 1640, 1600 cm-1.
trans-2-Amino-3-cyano-4-(3,4-methylenedioxyphenyl)-1-phe-
nylcyclopent-2-en-1-ol (14d)
Compound 14d was obtained from 12d as a pale yellow crystal in
48% yield; mp 162-164°C.
1H NMR (CDCl3): d = 2.01-2.28 (1 H, dd, J 14.2, 7.5 Hz, C5-H),
2.34 (3 H, s, CH3), 2.54-2.61 (2 H, dd, J = 14.2, 7.3, C5-H, OH),
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PAPER
Samarium(II) Iodide-Promoted Intermolecular and Intramolecular Ketone-Nitrile
97
4.18-4.36 (1 H, dd, J = 7.5, 7.3 Hz, C4-H), 4.46 (2 H, br s, NH2),
7.11-7.41 (9 H, m, ArH).
MS (EI, 70 eV): m/z (%) = 290 (M+, 73), 272 (M - H2O, 100), 257
(34), 198 (8), 181 (7), 163 (16), 155 (12), 154 (8), 119 (52), 91 (36).
References
(1) For reviews, see:
(a) Molander, G. A.; Harris, C. R. Chem. Rev. 1996, 96, 307.
(b) Matsuda, F. Synth. Org. Chem. Jpn. 1995, 53, 987.
(c) Molander, G. A. Org. React. 1994, 46, 211.
(d) Imamota, T. Lanthanides in Organic Synthesis; Academic
Press: London, 1994; Chap. 4.
(e) Shibasaki, M.; Sasai, H. Synth. Org. Chem. Jpn. 1993, 51,
972.
(f) Molander, G. A. Chem. Rev. 1992, 92, 29.
(g) Curran, D. P.; Fevig, T. L.; Jasperse, C. P.; Totleben, M. J.
Synlett 1992, 943.
Anal. Calcd for C19H18N2O: C, 78.60; H, 6.25; N, 9.65. Found: C,
78.38; H, 5.98; N, 9.77.
trans-2-Amino-3-cyano-1-phenyl-4-(p-tolyl)cyclopent-2-en-1-ol
(14g)
Compound 14g was obtained from 12g as a white solid in 68%
yield; mp 166-68°C.
IR (KBr): n = 3450, 3370, 3260, 2190, 1670, 1620, 1520 cm-1.
1H NMR (CDCl3): d = 2.13-2.20 (1 H, dd, J = 14.3, 7.4 Hz, C5-H),
2.32 (3 H, s, CH3), 2.63-2.70 (1 H, dd, J = 14.3, 7.3 Hz, C5-H), 2.85
(1 H, br s, OH), 4.23-4.28 (1 H, dd, J = 7.4, 7.3, C4-H), 4.41 (2 H,
br s, NH2), 7.12-7.49 (9 H, m, ArH).
MS (EI, 70 eV): m/z (%) = 290 (M+, 41), 272 (M+ - H2O, 100), 257
(28), 198 (15), 181 (6), 163 (15), 155 (34), 154 (27), 119 (58), 91
(41).
(2) (a) Matsuda, F.; Sakai, T.; Okada, N.; Miyashita, M.
Tetrahedron Lett. 1998, 39, 863.
(b) Fukuzawa, S.; Seki, K.; Tatsuzawa, M.; Motoh, K. J. Am.
Chem. Soc. 1997, 119, 1482.
(c) Molander, G. A.; McWilliams, J. C. J. Am. Chem. Soc.
1997, 119, 1265.
(d) Corey, E. J.; Zheng, G. Z. Tetrahedron Lett. 1997, 38,
2045.
Anal. Calcd for C19H18N2O: C, 78.60; H, 6.25; N, 9.65. Found: C,
78.31; H, 5.96; N, 9.60.
(e) Kito, M.; Sakai, T.; Shirahama, H.; Miyashita M.;
Matsuda, F. Synlett 1997, 219.
(f) Molander, G. A.; Shakya, S. R. J. Org. Chem. 1996, 61,
5885.
(g) Machrouhi, F.; Hamann, B.; Namy, J.; Kagan, H. B.
Synlett 1996, 633.
(h) Molander, G. A.; McKie, J. A. J. Org. Chem. 1995, 60,
872.
(i)Kan, T.; Nara, S.; Ito, S.; Matsuda, F.; Shirahama, H. J.
Org. Chem. 1994, 59, 5111.
(j) Kan, T.; Hosokawa, S.; Nara, S.; Oikawa, M.; Ito, S.;
Matsuda, F.; Shirahama, H. J. Org. Chem. 1994, 59, 5532.
(k) Kawatsure, M.; Matsuda, F.; Shirahama, H. J. Org. Chem.
1994, 59, 6900.
(l) Molander, G. A.; McKie, J. A. J. Org. Chem. 1994, 59,
3186.
(m) Enholm, E. J.; Trivellas, A. Tetrahedron Lett. 1994, 35,
1627.
(n) Baldwin, J. E.; Mackemzie Turner, S. C.; Moloney, M. G.
Tetrahedron 1994, 50, 9411.
Crystallographic Data for Compounds 13c and 14c32
Crystals of 13c and 14c suitable for X-ray analysis were obtained by
crystallization from EtOH solution.
D a t a f o r 1 3 c : C18H15ClN2O (310.78), colorless; monoclinic;
space group C2/c: a = 24.416 (2), b = 12.215 (4), c = 10.772 (4) Å;
b = 97.78 (1)∞; V = 3183 (1) Å3; Z = 8; Dc = 1.297 g cm-3; F
(000) = 1296. Data were collected with a Rigaku AFC7R diffracto-
meter with w -scan technique, graphite - monochromated Mo-Ka ra-
diation (l = 0.71069Å, m = 0.242 mm-1) at 293K. 3028 reflections
were measured, of which 2953 were independent reflections with 2q
in the range of 6 to 50∞, 1071 reflections having I > 2s (I). The struc-
ture was solved by direct methods29 and expanded using Fourier
techniques.30 All non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were included but not refined. The final cycle of
full-matrix least-sequares refinement give R = 0.058 and
2
Rw = 0.054 with w = 1/s (F0), S = 1.36. The maximum and the
minimum peak on the final difference Fourier map corresponded to
0.26 and -0.26 e/Å3, respectively. All calculations were performed
using TEXSAN program package.31
(o) Baldwin, J. E.; Mackemzie Turner, S. C.; Moloney, M. G.
Tetrahedron 1994, 50, 9425.
(p) Weinges, K.; Schmidbauer, S. B.; Schick, H. Chem. Ber.
1994, 127, 1305.
D a t a f o r 1 4 c : C18H15ClN2O (310.78), colorless; orthorhombic;
space group Pbcn: a = 13.370 (5), b = 10.481 (5), c = 23.350 (6) Å;
V = 3272 (3) Å3; Z = 8; Dc = 1.262 g cm-3; F (000) = 1296. Data
were collected with a Rigaku AFC7R diffractometer with w-scan
(3) (a) Kawatsura, M.; Kishi, E.; Kito, M.; Sakai, T.; Shirahama,
H.; Matsuda, F. Synlett 1997, 479.
(b) Fuchs, J. R.; Mitchell, M. L.; Shabangi, M.; Flowers, II R.
A. Tetrahedron Lett. 1997, 38, 8157.
technique, graphite
-
monochromated Mo-Ka radiation
(l = 0.71069Å, m = 0.236 mm-1) at 293K. 3278 reflections were
measured with 2q in the range of 6 to 50∞, 1551 reflections having I
> 2s (I). The structure was solved by direct methods29 and expanded
using Fourier techniques.30 All non-hydrogen atoms were refined
anisotropically. hydrogen atoms were refined isotropically. The fi-
nal cycle of full-matrix least-sequares refinement give R = 0.048
and Rw = 0.051 with w = 1/s 2(F0), S = 1.54. The maximum and the
minimum peak on the final difference Fourier map corresponded to
0.20 and - 0.22 e/Å3, respectively. All calculations were performed
using TEXSAN program package.31
(c) Kan, T.; Hosokawa, S.; Nara, S.; Oikawa, M.; Ito, S.;
Matsuda, F.; Shirahama, H. J. Org. Chem. 1994, 59, 5532.
(d) Chiara, J. L.; Martín-Lomas, M. Tetrahedron Lett. 1994,
35, 2969.
(e) Chiara, J. L.; Cabri, W.; Hanessian, S. Tetrahedron Lett.
1991, 32, 1125.
(f) Uenishi, J.; Masuda, S.; Wakabayashi, S. Tetrahedron Lett.
1991, 32, 5097.
(g) Molander, G. A.; Kenny, C. J. Am. Chem. Soc. 1989, 111,
8236.
(h) Molander, G. A.; Kenny, C. J. Org. Chem. 1988, 53, 2132.
(i) Molander, G. A.; Kenny, C. Tetrahedron Lett. 1987, 28,
4367.
Acknowledgement
(4) (a) Cossy, J.; Belloti, D. Tetrahedron Lett. 1988, 29, 6113.
(b) Belloti, D.; Cossy, J.; Pete, J. P.; Portella, C. J. Org. Chem.
1986, 51, 4196.
We are grateful to the National Natural Science Foundation of Chi-
na (Project No. 29672007 and 29872010), the NSF of Zhejiang Pro-
vince, China and the Laboratory of Organometallic Chemistry,
Shanghai Institute of Organic Chemistry, Chinese Academy of Sci-
ence for financial support.
(c) Belloti, D.; Cossy, J.; Pete, J. P.; Portella, C. Tetrahedron
Lett. 1985, 26, 4591.
Synthesis 2000, No. 1, 91–98 ISSN 0039-7881 © Thieme Stuttgart · New York

98
L. Zhou et al.
PAPER
(5) (a) Kariv-Miller, E.; Maeda, H.; Lombardo, F. J. Org. Chem.
1989, 54, 4022.
(19)(a) Zhou, L. H.; Zhang,Y. M. J. Chem. Soc., Perkin Trans. 1
1998, 2899.
(b) Kariv-Miller, E.; Mahachi, T. J. J. Org. Chem. 1986, 51,
1041.
(b) Zhou, L. H.; Y. M. Zhang, J. Chem. Soc., Perkin Trans. 1
1998, 2399.
(c) Fox, D. P.; Little, R. D.; Baizer, M. M. J. Org. Chem. 1985,
50, 2202.
(c) Zhou, L. H.; Zhang, Y. M. Tetrahedron Lett. 1997, 38,
8063.
(d) Shono, T.; Nishiguchi, I.; Ohimizu, H.; Mitani, M. J. Am.
Chem. Soc. 1978, 100, 545.
(20) Inanaga, J.; Ishikawa, M.; Yamaguchi, M. Chem. Lett. 1987,
1485.
(6) (a) Fürstner, A.; Ernst, A.; Kraue, H.; Ptock, A. Tetrahedron
1996, 52, 7329.
(21) Hughes, A. D.; Simpkins, N. S. Synlett 1998, 967.
(22) Gao, J.; Hu, M. Y.; Chen, J. X.; Yuan, S.; Chen, W. X.
Tetrahedron Lett. 1993, 34, 1617.
(23) Hünig, S.; Wehner, G. Synthesis 1975, 391.
(24) Ogata, Y.; Sawaki, Y.; Shiroyama, M. J. Org. Chem. 1977, 42,
406.
(25) Sharp, D. B.; Miller, E. L. J. Am. Chem. Soc. 1952, 74, 5643.
(26) Ogata, Y.; Nagura, K. J. Org. Chem. 1975, 40, 318.
(27) Blatt, A. H. J. Am. Chem. Soc. 1934, 56, 2774.
(28) Creary, X.; Inocencio, P. A.; Underine, T. L.; Kostromin, R.
J. Org. Chem. 1985, 50, 1932.
(b) Fürstner, A.; Hupperts, A. J. Am. Chem. Soc. 1995, 117,
4468.
(c) Fürstner, A.; Ptock, A.; Weintritt, H.; Goddard, R.; Krüger,
C. Angew. Chem. 1995, 107, 725; Angew. Chem. Int. Ed. Engl.
1995, 34, 678.
(d) Fürstner, A.; Weintritt, H.; Hupperts, A. J. Org. Chem.
1995, 60, 6637.
(e) Fürstner, A.; Ernst, A. Tetrahedron 1995, 51, 773.
(f) Fürstner, A.; Seidel, G.; Gabor, B.; Kopiske, C.; Krüger,
C.; Mynott, R. Tetrahedron 1995, 51, 8875.
(g) Fürstner, A.; Seidel, G. Synthesis 1995, 63.
(h) Fürstner, A.; Hupperts, A.; Ptock, A.; Janssen, E. J. Org.
Chem. 1994, 59, 5215.
(29) Sheldrick, G. M. Crystallographic Computing 3, Oxford
University Press 1985; p 175.
(30) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W.
P.; Garcia-Granda, S.; Gould, R. O.; Smits, J. M. M.;
Smykalla, C. The DIRDIF program System Technical Report
of the Crystallography Laboratory, University of Nijmegen,
The Netherlands, 1992.
(i) McMurry, J. E. Chem. Rev. 1989, 89, 1513.
(j) Lenoir, D. Synthesis 1989, 883.
(k) Betschart, C.; Seebach, D. Chimia 1989, 43, 39.
(l) McMurry, J. E. Acc. Chem. Res. 1983, 16, 405.
(7) (a) Ikeda, T.; Yue, S.; Hutchinson, C. R. J. Org. Chem. 1985,
50, 5193.
(b) Sowinski, A. F.; Whitesides, G. M. J. Org. Chem. 1979,
44, 2369.
(8) (a) Fieser, L. F.; Fieser, M. Steroids, Reinhold Publishing:
New York, 1959; p 600.
(31) TEXSAN: Crystal Structure Analysis Packages, Molecular
Structure Corporation (1985 & 1992).
(32) Selected bonds and angles of 13c and 14c.
13c: O(1) - C(1) 1.425(6), N(1) - C(2) 1.338(7), N(2) - C(6)
1.156(7), C(1) - C(2) 1.528(8), C(1) - C(5) 1.535(8), C(1) -
C(13) 1.533(8), C(2) - C(3) 1.341(7), C(3) - C(4) 1.526(7),
C(3) - C(6) 1.417(8), C(4) - C(5) 1.533(7), C(4) - C(7)
1.503(8); O(1) - C(1) - C(2) 111.7(5), O(1) - C(1) - C(5)
112.2(5), O(1) - C(1) - C(13) 105.3(4), C(2) - C(1) - C(5)
101.8(4), C(2) - C(1) - C(13) 113.4(5), C(5) - C(1) - C(13)
112.7(5), N(1) - C(2) - C(1) 118.6(5), N(1) - C(2) - C(3)
131.0(5), C(1) - C(2) - C(3) 110.4(5), C(2) - C(3) - C(4)
112.9(5), C(2) - C(3) - C(6) 125.9(5), C(4) - C(3) - C(6)
121.1(5), C(3) - C(4) - C(5) 100.9(4), C(3) - C(4) - C(7)
113.9(5), C(5) - C (4) - C(7) 114.2(5), C(1) - C(5) - C(4)
107.2(5), N(2) - C(6) - C(3) 177.4(7).
(b) Nakanishi, K.; Goto, T.; Ito, S.; Natori, S.; Nozoe, S., Eds.;
Natural Products Chemistry, Vol. 1; Kodansha/Academic
Press: New York, 1974; p 421.
(9) Arcamone, F. Top. Antib. Chem. 1978, 2, 102.
(10) Murahashi, S. I.; Naota, T.; Hanaoka, H. Chem. Lett. 1993,
1767, and references cited therein.
(11) Hashiyama, T.; Morikawa, K.; Sharpless, K. B. J. Org. Chem.
1992, 57, 5067, and references cited therein.
(12) Davis, F. A.; Sheppard, A. C.; Chen, B.-C. Haque, M. S.
J. Am. Chem. Soc. 1990, 112, 6679, and references cited
therein.
(13) Yamamoto, Y.; Matsumi, D.; Itoh, K. J. Chem. Soc., Chem.
Commun. 1998, 875.
(14) Corey, E. J.; Pyne, S. G. Tetrahedron Lett. 1983, 24, 2821.
(15) (a) Molander, G. A.; Kenny, C. J. Am. Chem. Soc. 1989, 111,
8236.
14c: O(1) - C(2) 1.431(4), N(1) - C(1) 1.331(4), N(2) - C(6)
1.150(4), C(1) - C(2) 1.536(4), C(2) - C(3) 1.530(5), C(2) -
C(13) 1.511(5), C(1) - C(5) 1.353(4), C(4) - C(5) 1.521(4),
C(5) - C(6) 1.406(5), C(3) - C(4) 1.531(5), C(4) - C(7)
1.520(4); O(1) - C(2) - C(1) 106.8(3), O(1) - C(2) - C(3)
106.2(3), O(1) - C(2) - C(13) 112.1(3), C(1) - C(2) - C(3)
101.8(3), C(1) - C(2) - C(13) 114.4(3), C(3) - C(2) - C(13)
114.6(3), N(1) - C(1) - C(2) 120.7(3), N(1) - C(1) - C(5)
129.3(3), C(2) - C(1) - C(5) 109.7(3), C(1) - C(5) - C(4)
112.6(3), C(1) - C(5) - C(6) 124.2(3), C(4) - C(5) - C(6)
123.1(3), C(3) - C(4) - C(5) 101.0(3), C(5) - C(4) - C(7)
112.7(3), C(3) - C(4) - C(7) 116.0(3), C(2) - C(3) - C(4)
106.7(3), N(2) - C(6) - C(5) 179.4(4).
(b) Zhou, L.; Zhang, Y.; Shi, D. Tetrahedron Lett. 1998, 39,
8491.
(c) Molander, G. A.; Wolfe, C. N. J. Org. Chem. 1998, 63,
9031.
(16) (a) Shono, T.; Kise, N.; Fujimoto, T.; Tominaga, N.; Morita,
H. J. Org. Chem. 1992, 57, 7175.
(b) Shono, T.; Kise, N. Tetrahedron Lett. 1990, 31, 1303.
(17) (a) Kraus, G. A.; Wan, Z. Tetrahedron Lett. 1997, 38, 6509.
(b) Molander, G. A.; Kenny, C. J. Am. Chem. Soc. 1989, 111,
8236.
Article Identifier:
1437-210X,E;2000,0,01,0091,0098,ftx,en;F03999SS.pdf
(c) Kraus, G. A.; James, O. S. J. Org. Chem. 1989, 54, 77.
(18) Souppe, J.; Danon, L.; Namy, J.; Kagan, H. B. J. Organomet.
Chem. 1983, 250, 227.
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