Modification of the Tiemann rearrangement: One-pot synthesis of N,N-disubstituted cyanamides from amidoximes

Article abstract of DOI:10.1055/s-2000-6317

A three-stage one-pot synthetic procedure for transformation of amidoximes to N,N-disubstituted cyanamides in 70-92% yield is described.

Full text of DOI:10.1055/s-2000-6317

1148
PAPER
Modification of the Tiemann Rearrangement: One-Pot Synthesis of
N,N-Disubstituted Cyanamides from Amidoximes
Stanislav A. Bakunov,a# Alexey V. Rukavishnikov,b‡Alexey V. Tkachev*c
a Novosibirsk State University, Novosibirsk 630090, Russia
b Novosibirsk Institute of Organic Chemistry, Novosibirsk 630090, Russia
c Novosibirsk State University, Novosibirsk Institute of Organic Chemistry, 9 Acad. Lavrentjev Ave., Novosibirsk, 630090, Russia
Fax +7(3832)344752; E-mail: atkachev@nioch.nsc.ru
Received 13 December 1999; revised 7 March 2000
This allowed us to develop the three-stage one-pot syn-
Abstract: A three-stage one-pot synthetic procedure for transfor-
thetic procedure from amidoximes to N,N-disubstituted
mation of amidoximes to N,N-disubstituted cyanamides in 70-92%
cyanamides. A solution of an amidoxime and triethy-
yield is described.
lamine in CH2Cl2 is treated with an equimolar amount of
Key words: Tiemann rearrangement, phase-transfer catalysis, ami-
TsCl followed by addition of an alkyl halide, 30% aque-
doximes, cyanamides, alkylations
ous solution of NaOH and phase-transfer catalyst fol-
lowed by reflux. At the first stage of the reaction
sequence, an amidoxime 1 is transformed to the corre-
Cyanamides (RR’N-C∫N) have been widely employed as
sponding O-tosylated derivative 2 which is then rear-
intermediates in organic synthesis and as biomolecules
precursors. The CN-group can be easily removed from a
ranged (Tiemann rearrangement) to give the
monosubstituted cyanamide 3. Alkylation of 3 under
phase-transfer conditions affords the N,N-disubstituted
non-symmetrical cyanamide 4 (Scheme 1).
cyanamide, and hence it can be used as a protective group
in the syntheses of secondary and tertiary amines.1,2 On
the other hand, transformation of the CN-group leads to
different classes of organic compounds such as ureas, car-
bamates, heterocycles, etc.3,4 Direct alkylation of
OTs
NH2
OH
cyanamide1 or its salts,5 including the alkylation under
phase-transfer conditions,6 as well as reaction of phosgene
imminium salts with ammonia7 are the simplest methods
for the preparation of substituted cyanamides.
N
N
a
quantitative yields
R1
NH2
R1
1
2
However, despite of conciseness and simplicity of the re-
actions cited, these methods are not suitable for prepara-
tion of the most attractive non-symmetrical cyanamides
(RR’N-C∫N, RπR’). The latter compounds can be ob-
tained by treatment of tertiary or secondary amines with
cyanohalides.8 Among the other possible approaches to
the non-symmetrical cyanamides, the following methods
should be mentioned: cyanation of halogen amines,9 treat-
ment of secondary amines with 1-cyanobenzotriazole,10
and dehydration of N,N-disubstituted ureas.11
N
C
N
N
C
N
b
70-92%
R1
R2
R1
H
4
3
Reagents and conditions: a) TsCl/Et3N/CH2Cl2, 0 ∞C; b) R2-Hal/30%
aq NaOH/Et3N+CH2PhCl-, reflux
Scheme 1
In this paper we report a mild and convenient procedure
for the conversion of amidoximes to N,N-disubstituted cy-
anamides with the loss of one carbon atom from the ami-
doxime molecule. We focused on the Tiemann
rearrangement12 to generate the crucial monosubstituted
cyanamides that were alkylated afterwards. When heated
with arylsulfonyl halides in a pyridine solution followed
by acidic hydrolysis, amidoximes are known to form
monosubstituted ureas as a result of the Tiemann rear-
rangement, cyanamides being the stable intermediates in
this reaction. Despite their high lability in acidic media,
cyanamides remain invariable under basic conditions at
pH >10 due to deprotonation and formation of cyanamide
anion.13 We have found that formation of monosubstituted
cyanamides was possible under the action of a base in the
two-phase system in presence of a phase-transfer catalyst.
We found a number of aromatic, aliphatic and terpenic
amidoximes can be easily converted in good yields (40-
90%) to disubstituted cyanamides. The one-pot version of
the synthetic pathway was found to be the most suitable
one because many O-tosyl derivatives of amidoximes and
some cyanamides 3 are too unstable for isolation.
To study the new reaction sequence we have synthesized
a number of amidoximes of different structures: (a) the
simplest aliphatic and aromatic amidoximes without addi-
tional functions, (b) amidoximes of seco-terpenic nature
having additional functions or labile groups (cyclopropyl
group, carbon-carbon double bond, hydroxy and keto
groups). Two different methods were used to prepare
Synthesis 2000, No. 8, 1148–1159 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Modification of the Tiemann Rearrangement
1149
starting amidoximes. Scheme 2 shows the formation of Due to the presence of carbon-carbon double bonds capa-
the amidoximes by the addition of hydroxylamine to ni- ble of migration in the molecules 10 and 13, we used py-
triles.
ridinium chloride14 instead of traditionally applied
p-toluenesulfonic acid, to prepare 1,3-dioxalane deriva-
tives 11 and 14 from the corresponding oxonitriles of
seco-limonene and seco-caryophyllene types (Scheme 4).
5a R = PhCH2 (92%)
5b R = Ph (85%)
5c R = iso-Pr (79%)
5d R = n-Am (84%)
N
OH
a
R
C
N
R
C
The second method is the based-promoted cleavage of
O-acylated a-hydroxylamino oximes (Scheme 5). Deriva-
tives of seco-pinane type 1715 and seco-carane type 1616
were prepared by this method.
NH2
5
6
4
a
3
7
N
OH
1
NHOAc
C
N
C
R
R
2
OH−/dioxane
O
NH2
7,9 (58%)
6,8
ref. 15, 16
N
HO
OH
9
N
10
8,9 R =
6,7 R =
8
H2N
OH
11
NH2
N
Reagents and conditions: a) NH2OH•HCl/Na2CO3/95% aq EtOH, re-
flux, 21 h
The numbering of the C-atoms does not coincide with the numbering
of the system according to IUPAC and is given for NMR interpretati-
on only.
N
OH
OH
NH2
O
O
17
16
Scheme 5
Scheme 2
A number of amidoximes listed above were used in the
one-pot syntheses of N,N-disubstituted cyanamides. Test-
ing of different alkyl halides as alkylating agents at the
stage of transformation of unsubstituted cyanamides to
the N,N-disubstituted ones shows that only the most active
alkyl halides (methyl iodide and ethyl bromide, allyl and
benzyl halides) are suitable for the reaction. Our attempts
to use other alkyl halides (primary and secondary alkyl
chlorides, bromides and iodides) resulted in poor yields of
the corresponding disubstituted cyanamides, although
alkylation of monosubstituted cyanamides with these ha-
lides under phase transfer conditions was reported.6 The
list of N-disubstituted cyanamides synthesized is shown in
Scheme 6.
In the case of oxonitriles, protection of the carbonyl group
is required prior to the addition of hydroxylamine
(Scheme 3).
NH2
CN
CN
O
H+
OH
N
O
NH2OH
HO
OH
H+
O
O
Scheme 3
OH
N
C
N
1 C
H2N
N
O
O
O
O
3
14
13
2
15
a
b
12
4
11
6
7
83%
82%
H
H
10
H
H
H
H
5
8
9
11
12
10
O
O
O
O
9
7
2
1
C
NH2
OH
a
b
50%
C
10
8
3
72%
N
N
N
4
6
5
13
14
15
Reagents and conditions: a) HOCH2CH2OH/Py•HCl, reflux in benzene, 5-7 h; b) NH2OH•HCl/Na2CO3/95% aq EtOH, reflux, 21 h
The numbering of the C-atoms does not coincide with the numbering of the systems according to IUPAC and are given for NMR interpretation
only.
Scheme 4
Synthesis 2000, No. 8, 1148–1159 ISSN 0039-7881 © Thieme Stuttgart · New York

1150
S. A. Bakunov et al.
PAPER
1a
1
1
CN
a
R= CH3
1
3a 4a
CN
2
4
CN
F
R
1a
2a
1a 2a
3a
3
3
3
5
6
5a
N
N
N
2
2
3
4a
b
c
R= CH2-CH=CH2
4
4
5
N
2
R
R
3a
R
1a 2a
CN
5a
1
R= CH2-Ph
5
6
1a
2a
F
d
e
R= CH2-CH3
F
F
4a
20 a-d
21 a-c
18 a-c
19 a-c
3a
R= 2,6-difluorobenzyl
2a
F
1a
5a
f
R= pentafluorobenzyl
R= 3-phenoxybenzyl
1
F
F10a
5
5
4a
7a
NC
g
11a
3a
2a
5a
9a
6
6
R
R
N
R
4
5
4
8
3
3
6a
2
1
N
1
CN
N
6
3
7
8a
7
7
O
CN
1a
2
2
4
10
10
8
O
9
8
9
9
11 24 a-c,e-g
O
10
22 a-c
23 a-c, e-g
1) Zn - AcOH, reflux
2) HCl
5
4
1
6
R
R
4
R
5
CN
N
O
3
3
O
1
N
2
1
CN
2
7
7
NH × HCl
CN
2
2
3
13
12
6
14
9
15
1
N
R
10
3
HO
9
8
8
9
4
7
11
6
10
8
4
6
H
5
H
5
11
8
27 a,c 10
28 a,c,g
25 a,b,e-g
7
26 a,c
10
9
The numbering of the C-atoms does not coincide with the numbering of the systems according to IUPAC and are given for NMR interpretation
only.
Scheme 6
The method developed is useful for the preparation of dif-
formed on a silica gel column (100-200 mesh) and the solvents
ferent non-symmetric N,N-disubstituted cyanamides. For
example, the method allowed us to prepare easily N,N-di-
substituted (1R)-cis-chrysanthemyl amine derivatives
28a, 28c and 28g, which are of interest because of their in-
secticidal properties.
used as eluents were distilled prior to use.
Preparation of Amidoximes from Nitriles; General Procedure
Method A, Addition of Hydroxylamine to Nitriles: Powdered
Na2CO3 (1.0 g, 9.4 mmol) and NH2OH•HCl (0.65 g, 9.4 mmol)
were added to a solution of a nitrile (7.2 mmol) in 95% aq EtOH
(40 mL) and the reaction mixture was stirred under reflux for 7 h.
An additional amount of Na2CO3 (0.5 g) and NH2OH•HCl (0.33 g)
were added and the mixture was stirred under reflux for 7 h. Addi-
tional portions of Na2CO3 and NH2OH•HCl (as indicated above)
were added and the mixture was stirred under reflux for 7 h more.
The mixture was cooled to r.t., filtered, and concentrated in vacuum.
The residue was treated with Et2O (30 mL) and 1 M aq HCl (3 × 15
mL), the aqueous phase was separated, neutralized with ammonia,
saturated with NaCl and extracted with Et2O (2 × 15 mL). The com-
bined extracts were dried (MgSO4) and concentrated at reduced
pressure to give the crude product, which was then purified by col-
umn chromatography (silica gel, Et2O/light petroleum).
Yields, melting points, optical rotations and analytical
data (obtained both by HRMS and combustion analysis)
for the new compounds are listed in Table 1. IR, MS and
NMR spectral data for the compounds synthesized are
listed in Table 2.
Melting points were determined using a Kofler hot-stage. IR spectra
1
were recorded on a Specord M-80 spectrophotometer. H and 13C
NMR spectra were recorded for 5-10% solutions on a Bruker AC
1
200 spectrometer (200.13 MHz for H, 50.32 MHz for 13C and
188.28 MHz for 19F). Proton and carbon chemical shifts were calcu-
lated relative to the solvent signals used as the internal standards:
dH = 7.24 (CDCl3) and 3.31 (CD3OD); dC = 76.90 (CDCl3) and
49.00 (CD3OD), whereas 19F chemical shifts are based relative to
the internal standard (C6F6, dF = 0.00). Optical rotations were mea-
sured on a Polamat A polarimeter at 20-23 ∞C for solutions in
CHCl3. MS spectra were recorded on a Finnigan MAT 8200 mass
spectrometer using electron impact ionization technique (70 eV).
Elemental analyses were performed using a Hewlett Packard 185
and Carlo Erba 1106 analyzers. All reagents and solvents were of
commercial quality. Petroleum ether refers to the fraction that
boiled in the range 40-70 ∞C. Preparative chromatography was per-
The treatment of the simplest nitriles, phenylacetonitrile, benzoni-
trile, 3-methylbutyronitrile and hexanenitrile, afforded correspond-
ing amidoximes as yellowish viscous oils: N-hydroxy-2-
phenylacetamidine (5a, yield 92%), N-hydroxybenzamidine (5b,
85%), N-hydroxyisobutyramidine (5c, 79%), N-hydroxyhexanami-
dine (5d, 84%). All the above amidoximes gave satisfactory mi-
croanalyses: C±0.35%, H±0.39%, N±0.38%.
Homochrysanthemyl amidoxime 7 was synthesized from the corre-
sponding nitrile 6 as reported earlier.17 N-Hydroxy-2-[3-(2-hy-
droxy-2-methylpropyl)-2,2-dimethylcyclopropyl]acetamidine (9)
was prepared by the above method from the corresponding hydroxy
Synthesis 2000, No. 8, 1148–1159 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Modification of the Tiemann Rearrangement
1151
Table 1 Yields, Melting Points, Optical Rotation, HRMS and Analytical Data for the New Compounds.
HRMS (M+)
Calcd
Producta
Yield (%) mp (solvent)
[α]578
(CHCl3)
Molcular
Formula
Found
9
58
80–82°C
−24.0 (c = 3.33)
C11H22N2O2
197.1637b
197.1654b
(95% aq EtOH)
11
83
82
72
50
85
89
70
85
80
81
90
90
92
oil
oil
oil
oil
oil
oil
oil
oil
oil
oil
oil
oil
+74.0 (c = 5.43)
C17H27NO2
C15H26N2O2
C12H19NO2
C10H18N2O2
C5H10N2
277.2044
249.1975b
209.1417
181.1352b
98.0848
277.2042
249.1967b
209.1416
181.1341b
98.0844
12
+71.3 (c = 8.27)
14
–
–
–
–
–
–
–
–
–
–
–
15
18a
18b
18c
19a
19b
19c
20a
20b
20c
C7H12N2
124.1002
174.1156
126.1158
152.1301
202.1466
146.0848
172.1003
222.1163
124.1000
174.1157
126.1157
152.1313
202.1470
146.0844
172.1001
222.1157
C11H14N2
C7H14N2
C9H16N2
C13H18N2
C9H10N2
C11H12N2
C15H14N2
38–41°C
(hexane/EtOAc)
20d
21a
21b
21c
22a
22b
22c
23a
23b
23c
23e
23f
85
88
91
92
75
79
70
87
82
83
82
84
81
84
75
79
82
78
73
oil
oil
oil
oil
oil
oil
oil
oil
oil
oil
oil
oil
oil
oil
oil
oil
oil
oil
oil
–
C10H12N2
160.0988
132.0688
158.0836
208.1010
194.1417
220.1570
270.1734
194.1421
220.1576
270.1743
306.1484
360.1264
192.1629
218.1783
268.1942
304.1750
358.1467
210.1733
236.1887
160.1001
132.0687
158.0844
208.1000
194.1419
220.1576
270.1732
194.1419
220.1576
270.1732
306.1544
360.1261
192.1626
218.1783
268.1939
304.1751
358.1468
210.1732
236.1889
–
C8H8N2
–
C10H10N2
–
C14H12N2
+10.8 (c = 3.33)
+9.0 (c = 2.90)
+7.1 (c = 3.95)
−5.0 (c = 10.4)
−8.7 (c = 8.26)
−8.9 (c = 6.27)
−6.6 (c = 3.35)
−9.1 (c = 5.15)
+71.5 (c = 4.00)
+56.7 (c = 5.64)
+49.3 (c = 5.12)
+43.1 (c = 4.50)
+40.8 (c = 4.44
+16.1 (c = 2.12
+14.7 (c = 1.90)
C11H18N2O
C13H20N2O
C17H22N2O
C11H18N2O
C13H20N2O
C17H22N2O
C17H20N2OF2
C17H17N2OF5
C12H20N2
24a
24b
24c
24e
24f
C14H22N2
C18H24N2
C18H22N2F2
C18H19N2F5
C12H22N2O
C14H24N2O
25a
25b
Synthesis 2000, No. 8, 1148–1159 ISSN 0039-7881 © Thieme Stuttgart · New York

1152
S. A. Bakunov et al.
PAPER
Table 1 (continued)
HRMS (M+)
Calcd
Producta
Yield (%) mp (solvent)
[α]578
(CHCl3)
Molcular
Formula
Found
25e
77
63–65°C
+15.2 (c = 2.24)
C18H24N2OF2
322.1856
322.1856
(EtOAc/hexane)
25f
26a
26c
27a
27c
28a
80
72
70
78
70
81
oil
oil
oil
oil
oil
+14.7 (c = 1.88)
C18H21N2OF5
C11H18N2O
C17H22N2O
C16H26N2O
C22H30N2O
C11H22NCl
376.1575
194.1420
270.1743
262.2049
338.2365
–
376.1574
194.1419
270.1732
262.2045
338.2358
–
–
–
–
+60.1 (c = 9.76)
+74.1 (c = 0.43)
218–220°C
(EtOAc/MeCN)
28c
28g
83
68
204–206°C
(EtOAc/MeCN)
+60.2 (c = 1.29)
+42.8 (c = 2.15)
C17H26NCl
–
–
–
–
143–145°C
C23H30NOCl
(EtOAc/MeCN)
a Satisfactory microanalyses obtained: C 0.5, H 0.4, 0.5.
b The molecular ion has insufficient intensity, so the analysis was carried out for the ion M+− OH.
nitrile 8.18 4-[(1S,2R)-3,3-Dimethyl-2-(3-oxobutyl)cyclobutyl]-N-
hydroxypent-4-enamidine (12) and ( )-N-Hydroxy-4-methyl-3-(3-
oxobutyl)pent-4-enamidine (15) were prepared from the protected
compounds 11 and 14, correspondingly.
M aq HCl (15 mL), 0.5 M aq Na2CO3 solution (15 mL), brine (15
mL) and dried (Na2SO4). The solvent was removed under reduced
pressure to give the crude product which was then chromatographed
(silica gel, 5Æ20% Et2O in light petroleum) to give an analytical
sample of the corresponding N-substituted N-cyanamide.
4-{(1S,2R)-3,3-Dimethyl-2-[2-(2-methyl-1,3-dioxolan-2-
yl)ethyl]cyclobutyl}-pent-4-enenitrile (11)
The following N,N-disubstituted N-cyanamides were prepared ac-
cording to this procedure:
Method A, Using Py•HCl: A solution of 1019 (9.33 g, 40 mmol),
ethylene glycol (4.5 mL, 80 mmol) and Py•HCl (0.5 g, 4.8 mmol) in
benzene (120 mL) was allowed to reflux with a Dean-Stark water
separator until the starting ketone had disappeared (5-7 h). The sol-
vent was removed under reduced pressure and the residue was taken
up into Et2O (50 mL). The ethereal extract was then washed with 1
M HCl (10 mL), 0.5 M aq Na2CO3 solution (10 mL), brine (10 mL),
and dried (MgSO4). The solvent was removed in vacuum and the
crude product was then purified by column chromatography to give
11 (9.20 g, 83%) as a viscous colorless oil.
Isopropylmethylcyanamide (18a), allylisopropylcyanamide (18b),
benzylisopropylcyanamide (18c), methylpentylcyanamide (19a),
allylpentylcyanamide (19b), benzylpentylcyanamide (19c), benzyl-
methylcyanamide (20a), allylbenzylcyanamide (20b), dibenzylcy-
anamide (20c), benzylethylcyanamide (20d), methylphenyl-
cyanamide (21a), allylphenylcyanamide (21b), benzylphenyl-
cyanamide (21c), [(1R,3S)-3-acetyl-2,2-dimethylcyclobutylmeth-
yl]methylcyanamide (22a), [(1R,3S)-3-acetyl-2,2-dimethylcyclo-
butylmethyl]allylcyanamide (22b), [(1R,3S)-3-acetyl-2,2-dimeth-
ylcyclobutylmethyl]benzylcyanamide (22c), [(1R,3S)-2,2-dimeth-
yl-3-(2-oxopropyl)cyclopropylmethyl]methylcyanamide (23a), al-
lyl[(1R,3S)-2,2-dimethyl-3-(2-oxopropyl)cyclopropylmethyl]-cy-
anamide (23b), benzyl[(1R,3S)-2,2-dimethyl-3-(2-oxopropyl)
[(1R,3S)-2,2-dimethyl-3-(2-oxopropyl)cyclopropylmethyl]cyan-
amide (23e), [(1R,3S)-2,2-dimethyl-3-(2-oxopropylcyclopropyl-
methyl]pentafluorophenylmethylcyanamide (23f), [(1R,3S)-2,2-
dimethyl-3-(2-oxopropyl)cyclopropylmethyl]-(3-phenoxybenzyl)-
cyanamide (23g, yield 80%, described earlier17), [(1R,3S)-2,2-dim-
ethyl-3-(2-methylpropenyl)cyclopropylmethyl]methylcyanamide
(24a), allyl[(1R,3S)-2,2-dimethyl-3-(2-methylpropenyl)cyclopro-
pylmethyl]cyanamide (24b), benzyl[(1R,3S)-2,2-dimethyl-3-(2-
methylpropenyl)cyclopropylmethyl]cyanamide (24c), (2,6-difluo-
robenzyl)-[(1R,3S)-2,2-dimethyl-3-(2-methylpropenyl)cyclopro-
pylmethyl]cyanamide (24e), [(1R,3S)-2,2-dimethyl-3-(2-methyl-
propenyl)cyclopropylmethyl]pentafluorophenylmethylcyanamide
(24f), [(1R,3S)-2,2-dimethyl-3-(2-methylpropenyl)cyclopropylme-
thyl]-(3-phenoxy-benzyl)cyanamide (24g, yield 82%, described
earlier17), [(1R,3S)-3-(2-hydroxy-2-methylpropyl)-2,2-dimethylcy-
clopropylmethyl]methylcyanamide (25a), allyl[(1R,3S)-3-(2-hy-
droxy-2-methylpropyl)-2,2-dimethylcyclopropylmethyl]cyan-
( )-4-Methyl-3-[2-(2-methyl-1,3-dioxolan-2-yl)-ethyl]-pent-4-
enenitrile (14) was prepared by the same method from the corre-
sponding keto nitrile 13 whose synthesis was described in Ref.19
Method B, Base-Promoted Cleavage of O-Acylated a-Hy-
droxyamino Oximes: Keto amidoximes 17 and 16 were prepared
from a-pinene ([a]D +20.0) and 3-carene ([a]D +16.0) via the corre-
sponding monoacylated derivatives according to Ref.15,16
Preparation of Cyanamides from Amidoximes; General Proce-
dure
A solution of TsCl (0.92 g, 4.8 mmol) in CH2Cl2 (15 mL) was added
dropwise during 1 h to a cooled (0 ∞C) stirred solution of an ami-
doxime (4.8 mmol) and Et3N (0.7 mL, 4.8 mmol) in CH2Cl2
(15 mL). The reaction mixture was allowed to warm to r.t. and
stirred for 1 h more. An alkyl halogenide (9.6 mmol, 2 equiv), 30%
aq solution of NaOH (20 mL) and BzEt3NCl (0.05 g) were added
and the mixture was stirred under reflux for 1 h, then cooled to r.t.,
poured into H2O (50 mL), and extracted with CH2Cl2 (2 × 15 mL).
The combined organic extracts were washed with H2O (15 mL), 1
Synthesis 2000, No. 8, 1148–1159 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Modification of the Tiemann Rearrangement
1153
Table 2 IR, MS and NMR Spectral Data for the Compounds Synthesized
Prod-
uct
IR (CHCl3)
MS
m/z (%)
1H NMRa,b
d, J, W1/2 (Hz)
13C NMRa,c
d, J (Hz)
n (cm−1)
9
3505 (OH),
3478, 3400
(NH2), 1658
(C=N), 1605,
1365, 1147
197 (2, M+ −
OH), 155 (100),
81 (48), 69 (35),
43 (86)
0.68−0.85 (m, 2 H, 3-H and 7-H), 0.87 (s, 6-H3),
1.03 (s, 5-H3), 1.20 (s, 10-H3), 1.21 (s, 11-H3),
1.35−1.50 (m, 2 H, 8-H2), 1.90−2.20 (m, 2 H, 2-H2),
4.72 (br, NH2, OH)
15.22 (q, C-6), 16.50 (s, C-4),
21.82 (d, C-7 or C-3), 23.12 (d, C-
3 or C-7), 26.26 (t, C-2), 28.21 (q,
C-11), 28.61 (q, C-5), 30.66 (q, C-
10), 37.38 (t, C-8), 70.64 (s, C-9),
153.99 (s, C-1)
11
2260 (C=N),
1640, 1470,
1390
277 (4, M+), 262
(40), 234 (4),
170 (85), 155
(45), 115 (40),
108 (66), 93
(46), 91 (330,
87 (100)
0.95 (s, 6 H, 9-H3 and 10-H3), 1.18 (s, 3 H, 15-H3),
1.3−1.6 (m, 5 H), 1.65−1.80 (m, 2 H), 2.15-2.50 (m,
5 H), 3.81 (s, 4 H, OCH2CH2O), 4.68 (br s W1/2 = 4,
1 H, 5-Ha), 4.80 (br s W1/2 = 4, 1 H, 5-Hb)
15.59 (t, C-2), 21.82 (q, C-9),
23.28 (q, C-15), 24.77 (t, C-12),
29.72 (t, C-3), 30.81 (q, C-10),
33.42 (s, C-8), 37.00 (t, C-13),
39.18 (t, C-7), 40.86 (d, C-6),
48.43 (d, C-11), 64.21 (t, 2 C,
OCHCH2O), 108.56 (t, C-5),
109.44 (s, C-14), 119.07 (s, C-1),
148.41 (s, C-4)
12
3605 (OH),
3520, 3415
(NH), 1710
(C=O), 1640
(C=N), 1620,
1585 (C=C),
910
249 (14, M+ −
OH), 209 (18),
193 (49), 167
(60), 136 (62),
124 (87), 110
(100), 95 (54),
83 (78)
0.97 (s, 6 H, 9-H3 and 10-H3), 1.36 (t, J = 10.5, 1 H,
7-Ha), 1.50−1.80 (m, 4 H, 7-Hb, 12-H2, 11-H), 2.04
(s, 3 H, 15-H3), 2.18−2.40 (m, 7 H, 2-H2, 3-H2, 6-H,
13-H2), 4.63 (br s, W1/2 = 12, NH2), 4.68 (br s W1/2
= 4, 1 H, 5-Ha), 4.70 (br s, W1/2 = 4, 1 H, 5-Hb), 8.51
(br, W1/2 = 20, NOH)
22.13 (q, C-9), 24.38 (t, C-12),
29.47 (t, C-3), 29.61 (q, C-15),
30.81 (q, C-10), 31.06 (t, C-2),
33.34 (s, C-8), 39.47 (t, C-7), 41.16
(d, C-6), 41.72 (t, C-13), 47.60 (d,
C-11), 107.37 (t, C-5), 151.12 (s,
C-4), 153.58 (s, C-1), 208.89 (s, C-
14)
14
15
2260 (C≡N),
1645 (C=C),
890
209 (33, M),
194 (31), 181
(100), 121 (18),
108 (19), 95
(28), 81 (27), 55
(13)
1.27 (s, 3 H, 10-H3), 1.57 (m, 4 H, 7-H2, 8-H2), 1.69
(br s, 3 H, 6-H3), 2.36−2.61 (m, 3 H, 2-H2, 3-H),
3.91 (m, 4 H, OCH2CH2O), 4.86 (br s, W1/2 = 3.5, 1
H, 5-Ha), 4.90 (dq, J = 1.5, 1.5, 1 H, 5-Hb)
18.81 (q, C-6), 22.43 (t, C-2),
24.11 (q, C-10), 27.52 (t, C-7),
37.29 (t, C-8), 44.70 (d, C-3),
65.56 (t, 2 C, OCH2CH2O), 110.71
(s, C-9), 114.04 (t, C-5), 120.02 (s,
C-1), 145.87 (s, C-4)
3605 (OH),
3520, 3420,
1710 1665,
1585, 1380,
900
181 (100, M+ −
OH), 122 (19),
108 (14), 95
(26), 81 (25), 55
(11), 42(18),
41(13)
1.30−1.70 (m, 2 H), 1.58 (s, 3 H, 6-H3), 2.04 (s, 3
H, 10-H3), 2.10−2.30 (m, 2 H), 2.50 (m, 3 H), 4.60
(br s, W1/2 = 10, 2 H, NH2), 4.69 (s, 1 H, 5-Ha), 4.73
(s, 1 H, 5-Hb), 8.0 (br, W1/2 = 25, 1 H, OH)
18.16 (q, C-6), 25.92 (t, C-7),
29.75 (q C-10), 35.15 (t, C-2),
40.72 (t, C-8), 43.80 (d, C-3),
112.77 (t, C-5), 145.84 (s, C-4),
152.68 (s, C-1), 208.71 (s, C-9)
18a
18b
2210 (C≡N),
1465, 1455,
1392, 1367,
1090
98.08480 (59,
M+), 83 (83), 57
(38), 56 (41), 43
(100), 41 (45)
1.24 (d, J = 6.5, 6 H, 3-H6), 2.86 (s, 3 H, 1a-H3),
3.19 (sept, J = 6.5, 1 H, 2-H)
20.20 (q, 2 C, C-3), 37.26 (q, C-
1a), 54.26 (d, C-2), 118.42 (s, C-1)
2220 (C≡N),
1455, 1412,
1393, 1360,
1180, 1090,
990, 935
124 (24, M+),
109 (45), 81 (5),
69 (6), 55 (33),
43 (28), 41
1.24 (d, J = 6.5, 6 H, 3-H6), 3.24 (sept, J = 6.5, 1 H,
2-H), 3.68 (ddd, J = 6.5, 1.5, 1.5, 2 H, 1a-H2), 5.30
(ddt, J = 10.5, 1.5, 1.5, 1 H, 3a-Ha), 5.33 (ddt, J =
17.0, 1.5, 1.5, 1 H, 3a-Hb), 5.90 (ddt, J = 17.0, 10.5,
6.5, 1 H, 2a-H)
20.84 (q, 2 C, C-3), 53.02 (d, C-2),
53.86 (t, C-1a), 117.39 (s, C-1),
119.96 (t, C-3a), 133.37 (d, C-2a)
(100)
18c
19a
2220 (C≡N),
1495, 1450,
1362, 1165,
703
174 (16, M+),
159 (4), 131 (2),
91 (100), 77 (3),
65 (11), 41 (5)
1.19 (d, J = 6.5, 6 H, 3-H6), 3.27 (sept, J = 6.5 Hz,
1 H, 2-H), 4.18 (s, 2 H, 1a-H2), 7.33 (m, 5 H, Ar-H)
20.77 (q, 2C, C-3), 52.93 (d, C-2),
55.18 (t, C-1a), 117.69 (s, C-1),
129.39 (d, C-5a), 129.60 (d, 2 C,
C-3a), 129.91 (d, 2 C, C-4a),
137.00 (s, C-2a)
2220 (C≡N),
1370, 1180
126 (13, M+),
111 (12), 97
(16), 83 (9), 69
(100), 57 (15),
44 (35)
0.95 (t, J = 6.5, 3 H, 6-H3), 1.25-1.41 (m, 4 H, 5-H2
and 4-H2), 1.65 (m, 2 H, 3-H2), 2.87 (s, 3 H, 1a-H3),
3.05 (t, J = 6.5, 2 H, 2-H2)
14.33 (q, C-6), 23.28 (t, C-5),
27.98 (t, C-3), 29.63 (t, C-4), 39.07
(q, C-1a), 53.73 (t, C-2), 119.79 (s,
C-1)
Synthesis 2000, No. 8, 1148–1159 ISSN 0039-7881 © Thieme Stuttgart · New York

1154
S. A. Bakunov et al.
PAPER
Table 2 (continued)
Prod-
uct
IR (CHCl3)a
MS
m/z (%)
1H NMRb
d, J, W1/2 (Hz)
13C NMRb,c
d, J (Hz)
n (cm−1)
19b
2205 (C∫N),
1460, 1380,
930
152 (6, M+), 137
(14), 123 (7), 95
(31), 70 (22), 55
(19), 41 (100)
0.75 (t, J = 6.5, 3 H, 6-H3), 1.05-1.20 (m, 4 H, 4-H2
and 5-H2), 1.40 (m, 2 h, 3-H2), 2.74 (t, J = 6.5, 2 H,
2-H2), 3.39 (ddt, J = 6.5, 1.0, 1.0, 2 H, 1a-H), 5.07
(ddt, J = 10.5, 1.0, 1.0, 1 H, 3a-Ha), 5.10 (ddt, J =
17.0, 1.0, 1.0, 1 H, 3a-Hb), 5.62 (ddt, J = 17.0, 10.5,
6.5, 1 H, 2a-H)
13.28 (q, C-6), 21.59 (t, C-5),
26.61 (t, C-3), 27.95 (t, C-4), 50.02
(t, C-2), 53.71 (t, C-1a), 115.94 (s,
C-1), 119.00 (t, C-3a), 130.98 (d,
C-2a)
19c
2205 (C∫N),
1450, 1165,
1090
202 (7, M+), 201
(12), 111 (10),
91 (100), 83 (5),
69 (35), 65 (9),
44 (13)
0.79 (t, J = 6.5, 3 H, 6-H3), 1.10-1.30 (m, 4 H, 5-H2
and 4-H2), 1.49 (m, 2 H, 3-H2), 2.74 (t, J = 6.5, 2 H,
2-H2), 4.00 (s, 2 H, 1a-H2), ª7.2 (m, 5 H, Ar-H)
13.43 (q, C-6), 21.70 (t, C-5),
26.61 (t, C-3), 28.09 (t, C-4), 49.72
(t, C-2), 55.34 (t, C-1a), 116.49 (s,
C-1), 127.82 (d, C-5a), 127.87 (d,
C-4a), 128.24 (d, 2 C, C-3a),
134.67 (s, C-2a)
20a
20b
2220 (C∫N),
1460, 1380,
1038
146 (22, M+),
104 (3), 91
(100), 65 (13),
39 (6)
2.74 (s, 3 H, 1a-H3), 4.12 (s, 2 H, 2-H2), ª7.34 (m,
37.63 (q, C-1a), 56.98 (t, C-2),
118.63 (s, C-1), 128.20 (d, C-6),
128.41 (d, C-4), 128.71 (d, C-5),
134.19 (s, C-3)
5 H, Ar-H)
2220 (C∫N),
1500, 1460,
1385, 1000,
942
172 (6, M+), 160
(2), 130 (2), 117
(2), 92 (14), 91
(100), 77 (2), 65
(10), 51 (3)
3.53 (ddd, J = 7, 1.5, 1.5, 2 H, 1a-H2), 4.15 (s, 2 H,
2-H2), 5.27 (ddt, J = 17.0, 1.5, 1.5, 1 H, 3a-Ha), 5.31
(ddt, J = 11.0, 1.5, 1.5, 1 H, 3a-Hb), 5.82 (ddt, J =
17.0, 11.0, 7, 1 H, 2a-H), ª7.34 (m, 5 H, Ar-H)
52.88 (t, C-1a), 54.58 (t, C-2),
117.70 (s, C-1), 120.54 (t, C-3a),
128.37 (d, C-6), 128.38 (d, 2 C, C-
5), 128.74 (d, 2 C, C-4), 130.66 (d,
C-2a), 134.39 (s, C-3)
20c
2200 (C∫N),
1465, 1250,
1000, 725
222.11625 (7,
M+), 131 (19),
92 (10), 91
(100), 65 (15),
28 (20)
4.07 (s, 4 H, 2-H2 and 1a-H2), ª7.30 (m, 10 H, Ar-
H)
54.16 (t, 2 C, C-2 and C-1a),
117.64 (s, C-1), 128.52 (d, 2 C, C-
6 and C-5a), 128.53 (d, 4C, C-4
and C-3a), 128.79 (d, 4C, C-5 and
C-4a), 134.33 (s, 2 C, C-3 and C-
2a)
20d
21a
21b
2200 (C∫N),
1495, 1460,
1385, 1155,
1080
160 (16, M+),
146 (4), 117 (2),
104 (2), 91
(100), 77 (3), 65
(10), 51 (3)
1.23 (t, J = 7, 3 H, 2a-H3), 2.96 (q, J = 7, 2 H, 1a-
H2), 4.16 (s, 2 H, 2-H2), ª7.32 (m, 5 H, Ar-H)
12.49 (q, C-2a), 44.95 (t, C-1a),
55.44 (t, C-2), 117.52 (s, C-1),
128.18 (d, C-6), 128.71 (d, 2 C, C-
5), 128.32 (d, 2 C, C-4), 134.74 (s,
C-3)
2216 (C∫N),
1595, 1495,
1385, 1105
132 (100, M+),
117 (14), 91
(43), 77 (33), 65
(26), 51 (21), 42
(36)
3.22 (s, 3 H, 1a-H3), ª7.04 (m, 3 H, 3-H2 and 5-H),
ª7.32 (m, 2 H, 4-H2)
37.18 (q, C-1a), 115.17 (s, C-1),
115.86 (d, 2 C, C-3), 124.28 (d, C-
5), 130.57 (d, 2 C, C-4), 141.68 (s,
C-2)
2220 (C∫N),
1598, 1497,
1360, 1190
158 (76, M+),
131 (59), 130
(51), 118 (19),
91 (15), 77 (38),
65 (18), 51 (26),
41 (100)
4.26 (ddd, J = 6.0, 1.5, 1.5, 2 H, 1a-H2), 5.33 (ddt,
J = 10.5, 1.5, 1.5, 1 H, 3a-Hb), 5.36 (ddt, J = 17.0,
1.5, 1.5, 1 H, 3a-Ha), 5.96 (ddt, J = 17.0, 10.5, 6.0,
1 H, 2a-H), ª7.08 (m, 3 H, 3-H2 and 5-H), ª7.29 (m,
2 H, 4-H2)
52.99 (t, C-1a), 114.70 (s, C-1),
117.08 (d, 2 C, C-3), 119.98 (t, C-
3a), 124.79 (d, C-5), 130.72 (d, 2
C, C-4), 131.91 (d, C-2a), 141.15
(s, C-2)
21c
22a
2222 (C∫N),
1595, 1492,
1360, 740
208 (17, M+), 91
(100), 77 (5), 65
(17), 28 (64)
4.83 (s, 2 H, 1a-H2), 7.05-7.25 (m, 3 H, Ar-H),
7.30-7.45 (m, 7 H, Ar-H)
54.43 (t, C-1a), 115.03 (s, C-1),
117.43 (d, 2 C), 124.94 (d), 128.88
(d, 2 C), 129.48 (d), 129.95 (d, 2
C), 130.75 (d, 2 C), 136.09 (s),
141.22 (s)
2220 (C∫N),
1700 (C=O),
1475, 1460,
1385, 1370,
910
194 (1, M+), 179
(4), 151 (13),
123 (13), 109
(25), 99 (19), 83
(460), 69 (100),
43 (80)
0.84 (s, 3 H, 6-H3), 1.32 (s, 3 H, 5-H3), 1.80-2.05
(m, 2 H), 1.99 (s, 3 H, 10-H3), 2.30 (m, 1 H), 2.70-
3.15 (m, 3 H), 2.77 (s, 3 H, 1a-H3)
16.94 (q, C-6), 20.94 (t, C-7),
30.05 (q, C-10), 30.32 (q, C-5),
38.81 (d, C-3), 39.09 (q, C-1a),
42.39 (s, C-4), 53.22 (d, C-8),
53.16 (t, C-2), 118.09 (s, C-
1),206.92 (s, C-9)
Synthesis 2000, No. 8, 1148–1159 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Modification of the Tiemann Rearrangement
1155
Table 2 (continued)
Prod-
uct
IR (CHCl3)a
MS
m/z (%)
1H NMRb
d, J, W1/2 (Hz)
13C NMRb,c
d, J (Hz)
n (cm−1)
22b
2205 (C∫N),
1700 (C=O),
1365, 1354,
938
220 (1, M+), 205
(5), 177 (15),
149 (15), 135
(16), 123 (16),
99 (17), 95 (27),
83 (40), 81 (25),
43 (78), 41
0.91 (s, 3 H, 6-H3), 1.39 (s, 3 H, 5-H3), 1.76-2.01
(m, 2 H), 2.05 (s, 3 H, 10-H3), 2.34 (m, 1 H), 2.96
(dd, J = 13.0, 7.0, 1 H, 2-Ha), 3.01 (dd, J = 13.0,
8.0, 1 H, 2-Hb), 3.11 (m, 1 H), 3.66 (ddt, J = 6.5, 1.5,
1.5, 2 H, 1a-H2), 5.27 (ddt, J = 11, 1.5, 1.5, 1 H, 3a-
Hb), 5.33 (ddt, J = 17.0, 1.5, 1.5, 1 H, 3a-Ha), 5.86
(ddt, J = 17.0, 11.0, 7.0, 1 H, 2a-H)
17.49 (q, C-6), 22.29 (t, C-7),
30.36 (q, C-10), 30.77 (q, C-5),
40.51 (d, C-3), 43.69 (s, C-4),
54.31 (d, C-8), 52.43 (t, C-2),
55.38 (t, C-1a), 118.74 (s, C-1),
120.49 (t, C-3a), 132.69 (d, C-2a),
209.71 (s, C-9)
(100)
22c
2210 (C∫N),
1700 (C=O),
1460, 1360
270 (6, M+), 269
(12), 255 (2),
199 (6), 132 (5),
91 (100), 83
(11), 81 (9), 69
(24), 43 (26), 41
(15)
0.77 (s, 3 H, 6-H3), 1.32 (s, 3 H, 5-H3), 1.80-2.05
(m, 2 H), 1.98 (s, 3 H, 10-H3), 2.30 (m, 1 H), 2.70-
3.15 (m, 3 H), 4.10 (s, 2 H, 1a-H2), ª7.30 (m, 5 H,
Ar-H)
16.84 (q, C-6), 20.59 (t, C-7),
30.00 (q, C-10), 30.24 (q, C-5),
38.80 (d, C-3), 42.34 (s, C-4),
50.55 (t, C-2), 53.16 (d, C-8),
56.04 (t, C-1a), 117.46 (s, C-1),
128.17 (d, 2C), 128.35 (d, C-5a),
128.65 (d, 2 C), 134.35 (s, C-2a),
206.87 (s, C-9)
23a
23b
2220 (C∫N),
1720 (C=O),
1370, 1180
194 (2, M+), 179
(2), 139 (100),
81 (48), 69 (35),
43 (86)
0.75-0.95 (m, 2 H, 3-H and 7-H), 0.82 (s, 3 H, 6-
H3), 0.98 (s, 3 H, 5-H3), 2.00 (s, 3 H, 10-H3), 2.27
(d, J = 7.0, 2 H, 8-H2), 2.68 (s, 3 H, 1a-H3), 2.73 (dd,
J = 14.0, 8.0, 1 H, 2-Ha), 2.82 (dd, J = 14.0, 7.0, 1
H, 2-Hb)
14.49 (q, C-6), 17.88 (s, C-4),
21.48 (d, C-7 or C-3), 22.82 (d, C-
3 or C-7), 27.87 (q, C-5), 29.18 (q,
C-10), 38.12 (q, C-1a), 38.66 (t, C-
8), 49.36 (t, C-2), 118.04 (s, C-1),
207.27 (s, C-9)
2220 (C∫N),
1715 (C=O),
1375
220 (1, M+), 205
(3), 139 (42), 81
(24), 43 (100),
41 (37)
0.75-1.00 (m, 2 H, 3-H and 7-H), 0.83 (s, 3 H, 6-
H3), 1.00 (s, 3 H, 5-H3), 2.01 (s, 3 H, 10-H3), 2.27
(dd, J = 17.0, 8.0, 1 H, 8-Ha), 2.29 (dd, J = 17.0, 7.0,
1 H, 8-Hb), 2.76 (dd, J = 13.5, 8.0, 1 H, 2-Ha), 2.84
(dd, J = 13.5, 7.0, 1 H, 2-Hb), 3.48 (d, J = 7.0, 2 H,
1a-H2), 5.15 (dd, J = 11.0, 1.5, 1 H, 3a-Ha), 5.16
(dd, J = 17.0, 1.5, 1H), 5.70 (ddt, J = 17.0, 11.0, 7.0,
1 H, 2a-H)
14.53 (q, C-6), 17.96 (s, C-4),
21.57 (d, C-7 or C-3), 23.03 (d, C-
3 or C-7), 27.91 (q, C-5), 29.20 (q,
C-10), 38.72 (t, C-8), 47.32 (t, C-
2), 53.64 (t, C-1a), 117.13 (s, C-1),
119.59 (t, C-3a), 130.70 (d, C-2a),
207.25 (s, C-9)
23c
2220 (C∫N),
1715 (C=O),
1380, 920
270 (5, M+), 139
(77), 121 (14),
91 (100), 81
0.80-1.00 (m, 2 H, 3-H and 7-H), 0.87 (s, 3 H, 6-
H3), 1.08 (s, 3 H, 5-H3), 2.08 (s, 3 H, 10-H3), 2.26
(dd, J = 17.5, 8.0, 1 H, 8-Ha), 2.32 (dd, J = 17.5, 7.0,
1 H, 8-Hb), 2.82 (dd, J = 13.0, 8.0, 1 H, 2-Ha), 2.88
(dd, J = 13.0, 7.0, 1 H, 2-Hb), 4.13 (s, 2 H, 1a-H2),
ª7.30 (s, 5 H, Ar-H)
14.72 (q, C-6), 18.26 (s, C-4),
21.79 (d, C-7 or C-3), 23.13 (d, C-
3 or C-7), 28.12 (q, C-5), 29.42 (q,
C-10), 38.92 (t, C-8), 47.22 (t, C-
2), 55.39 (t, C-1a), 117.78 (s, C-1),
128.02 (d, 2 C, C-3a or C-4a),
128.27 (d, C-5a), 128.65 (d, 2 C,
C-4a or C-3a), 134.61 (s, C-2a),
207.53 (s, C-9)
(16), 43 (66)
23e
2225 (C∫N),
1715 (C=O),
1630, 1595
(C=C), 1485,
1360, 1040
(C-F)
306 (4, M+), 287
(3), 263 (4), 139
(68), 127 (100),
95 (15), 81 (21),
43 (93)
0.65-0.90 (m, 2 H, 3-H and 7-H), 0.75 (s, 3 H, 6-
H3), 0.93 (s, 3 H, 5-H3), 1.94 (s, 3 H, 10-H3), 2.18
(dd, J = 17.5, 8.0, 1 H, 8-Ha), 2.26 (dd, J = 17.5, 7.0,
1 H, 8-Hb), 2.78 (dd, J = 13.5, 8.0, 1 H, 2-Ha), 2.88
(dd, J = 13.5, 7.0, 1 H, 2-Hb), 4.08 (s, 2 H, 1a-H2),
6.76 (dd, JHH = 8.0, JHF = 8.0, 2 H, 4a-H2), 7.18 (tt,
JHH = 8.0, JHF = 1.5, 1 H, 5a-H)
14.17 (q, C-6), 17.90 (s, C-4),
21.54 (d, C-7 or C-3), 22.70 (d, C-
3 or C-7), 27.68 (q, C-5), 28.96 (q,
C-10), 38.38 (t, C-8), 42.07 (t, C-
1a), 47.53 (t, C-2), 110.26 (s, 2JCF
=
19.5, C-2a), 110.96 (d, 2JCF = 25.2,
C-4a), 116.18 (s, C-1), 130.49 (d,
3JCF = 10.4, C-5a), 161.07 (d, 1JCF
=
250.4, 3JCF = 7.3, C-3a), 207.04 (s,
C-9)
23f
2220 (C∫N),
1715 (C=O),
1660, 1530
(C=C), 1365,
1130, 1025
(C-F)
360 (1, M+), 342
(1), 317 (1), 303
(1), 181 (40),
139 (42), 123
(29), 95 (25), 81
(45), 43 (100)
0.80-1.10 (m, 2 H, 3-H and 7-H), 0.94 (s, 3 H, 6-
H3), 1.12 (s, 3 H, 5-H3), 2.13 (s, 3 H, 10-H3), 2.40
(d, J = 7.5, 2 H, 8-H2), 2.94 (dd, J = 13.0, 8.0, 1 H,
2-Ha), 3.02 (dd, J = 13.0, 7.0, 1 H, 2-Hb), 4.25 (t, JHF
= 1.5, 2 H, 1a-H2)
14.73 (q, C-6), 18.56 (s, C-4),
22.10 (d, C-7 or C-3), 23.13 (d, C-
3 or C-7), 28.13 (q, C-5), 29.50 (q,
C-10), 38.99 (t, C-8), 42.32 (t, C-
1a), 48.74 (t, C-2), 115.82 (s, C-1),
207.45 (s, C-9)
Synthesis 2000, No. 8, 1148–1159 ISSN 0039-7881 © Thieme Stuttgart · New York

1156
S. A. Bakunov et al.
PAPER
Table 2 (continued)
Prod-
uct
IR (CHCl3)a
MS
m/z (%)
1H NMRb
d, J, W1/2 (Hz)
13C NMRb,c
d, J (Hz)
n (cm−1)
24a
2205 (C∫N)
192 (33, M+),
177 (7), 136
(11), 123 (100),
121 (13), 95
(22), 93 (15), 81
(65), 69 (23), 43
(25)
ª0.86 (m, 1 H, 3-H), 0.87 (s, 3 H, 6-H3), 1.01 (s, 3
H, 5-H3), 1.28 (dd, J = 8.0, 8.0, 1 H, 7-H), 1.53 (d,
J = 1.5, 3 H, 10-H3 or 11-H3), 1.57 (d, J = 1.5, 3 H,
11-H3 or 10-H3), 2.69 (s, 3 H, 1a-H3), 2.72 (dd, J =
13.0, 9.0, 1 H, 2-Ha), 2.78 (dd, J = 13.0, 7.0, 1 H, 2-
Hb), 4.68 (dqq, J = 8.0, 1.5, 1.5, 1 H, 8-H)
15.01 (q, C-6), 18.05 (q, C-10),
19.92 (s, C-4), 25.21 (q, C-10),
25.53 (d, C-7 or C-3), 25.70 (d, C-
3 or C-7), 27.97 (q, C-5), 38.12 (q,
C-1a), 49.76 (t, C-2), 117.56 (s, C-
1), 117.91 (d, C-8), 135.23 (s, C-9)
24b
2205 (C∫N)
218 (9, M+), 203
(5), 136 (9), 123
(100), 121 (14),
105 (12), 95
(21), 91 (22), 81
(49), 69 (19), 41
(49)
1.04 (s, 3 H, 6-H3), ª1.06 (m, 1 H, 3-H), 1.15 (s, 3
H, 5-H3), 1.49 (dd, J = 8.0, 8.0, 1 H, 7-H), 1.70 (d,
J = 1.5, 3 H, 10-H3 or 11-H3), 1.73 (d, J = 1.5, 3 H,
11-H3 or 10-H3), 2.98 (dd, J = 13.0, 8.0, 1 H, 2-Ha),
3.06 (dd, J = 13.0, 6.5, 1 H, 2-Hb), 3.65 (dm, J =
6.0, 2 H, 1a-H2), 4.90 (dqq, J = 8.0, 1.5, 1.5, 1 H,
8-H), 5.30 (ddt, J = 10.0, 1.5, 1.5, 1 H, 3a-Ha), 5.32
(ddt, J = 17.0, 1.5, 1.5, 1 H, 3a-Hb), 5.86 (ddt, J =
17.0, 10.0, 6.0, 1 H, 2a-H)
15.93 (q, C-6), 18.78 (q, C-10),
21.54 (s, C-4), 25.92 (d, C-7 or C-
3), 27.34 (q, C-11), 27.46 (d, C-3
or C-7), 28.85 (q, C-5), 49.31 (t, C-
2), 55.01 (t, C-1a), 118.84 (s, C-1),
119.55 (d, C-8), 120.05 (t, C-3a),
131.61 (d, C-2a), 136.79 (s, C-9)
24c
2200 (C∫N),
1580, 1485
268 (14, M+),
267 (9), 253 (6),
225 (4), 136 (8),
123 (100), 95
(13), 91 (50), 81
(29), 41 (17)
0.93 (s, 3 H, 6-H3), ª1.0 (m, 1 H, 3-H), 1.11 (s, 3 H,
5-H3), 1.42 (dd, J = 8.0, 8.0, 1 H, 7-H), 1.62 (d, J =
1.5, 3 H, 10-H3 or 11-H3), 1.65 (d, J = 1.5, 3 H, 11-
H3 or 10-H3), 2.82 (dd, J = 13.0, 8.0, 1 H, 2-Ha),
2.90 (dd, J = 13.0, 6.5, 1 H, 2-Hb), 4.11 (s, 2 H, 1a-
H2), 4.72 (dqq, J = 8.0, 1.5, 1.5, 1 H, 8-H), ª7.28
(m, 5 H, Ar-H)
15.20 (q, C-6), 18.26 (q, C-10),
20.28 (s, C-4), 25.43 (q, C-11),
25.89 (d, C-7 or C-3), 26.04 (d, C-
3 or C-7), 28.18 (q, C-5), 47.60 (t,
C-2), 55.35 (t, C-1a), 117.33 (s, C-
1), 118.13 (d, C-8), 127.84 (d, 2 C,
C-4a or C-5a), 128.01 (d, C-5a),
128.48 (d, 2 C, C-3a or C-4a),
134.93 (s, C-2a), 135.38 (s, C-8)
24e
2205 (C∫N),
1630, 1595
(C=C), 1480,
1370, 1030
(C-F)
304 (4, M+), 285
(5), 261 (8), 137
(6847), 127
(100), 95 (19),
81 (33), 43 (72)
ª0.9 (m, 1 H, 3-H), 0.93 (s, 3 H, 6-H3), 1.08 (s, 3 H,
5-H3), 1.40 (dd, J = 8.0, 8.0, 1 H, 7-H), 1.62 (d, J =
1.5, 3 H, 10-H3 or 11-H3), 1.64 (d, J = 1.5, 3 H, 11-
H3 or 10-H3), 2.92 (dd, J = 13.0, 8.0, 1 H, 2-Ha),
3.02 (dd, J = 13.0, 6.5, 1 H, 2-Hb), 4.11 (s, 2 H, 1a-
H2), 4.78 (dqq, J = 8.0, 1.5, 1.5, 1 H, 8-H), 6.75 (m
,2 H, 4a-H2), 7.30 (m, 1 H, 5a-H)
15.05 (q, C-6), 18.24 (q, C-10),
20.35 (s, C-4), 25.35 (q, C-11),
25.60 (d, C-7 or C-3), 26.04 (d, C-
3 or C-7), 28.03 (q, C-5), 42.39 (t,
C-1a), 48.25 (t, C-2), 111.00 (s,
2JCF = 20.1, C-2a), 111.25 (d, 2JCF
= 25.3, C-4a), 116.71 (s, C-1),
117.81 (d, C-8), 130.61 (d, 3JCF
=
10.3, C-5a), 135.90 (s, C-9),
161.23 (s, 1JCF = 250.5, 3JCF = 7.3,
C-3a)
24f
25a
25b
2205 (C∫N),
1660, 1530
(C=C), 1360,
1130, 1025
(C-F)
358 (1, M+), 340
(3), 315 (4), 301
(3), 181 (35),
139 (38), 123
(41), 95 (20), 81
(33), 43 (100)
1.00 (s, 3 H, 6-H3), ª1.1 (m, 1 H, 3-H), 1.15 (s, 3 H,
5-H3), 1.46 (dd, J = 8.0, 8.0, 1 H, 7-H), 1.67 (d, J =
1.5, 3 H, 10-H3 or 11-H3), 1.71 (d, J = 1.5, 3 H, 11-
H3 or 10-H3), 2.98 (dd, J = 13.0, 8.0, 1 H, 2-Ha),
3.02 (dd, J = 13.0, 6.5, 1 H, 2-Hb), 4.23 (br s, 2 H,
1a-H2), 4.78 (dqq, J = 8.0, 1.5, 1.5, 1 H, 8-H)
15.69 (q, C-6), 18.65 (q, C-10),
23.05 (s, C-4), 27.11 (d, C-7 or C-
3), 27.69 (q, C-11), 28.68 (d, C-3
or C-7), 28.98 (q, C-5), 43.51 (t, C-
2a), 50.01 (t, C-2), 117.60 (s, C-1),
119.22 (d, C-8), 137.22 (s, C-9)
3615 (OH),
2215 (C∫N)
210 (2, M+), 195
(2), 155 (100),
81 (48), 69 (35),
43 (86)
0.75-0.90 (m, 2 H, 3-H and 7-H), 0.95 (s, 3 H, 6-
H3), 1.09 (s, 3 H, 5-H3), 1.18 (s, 3 H, 10-H3), 1.19
(s, 3 H, 11-H3), 1.35 (dd, J = 14.0, 7.5, 1 H, 8-Ha),
1.42 (dd, J = 14.0, 5.0, 1 H, 8-Hb), 1.75 (br s, 1 H,
OH), 2.78 (dd, J = 13.0, 8.5, 1 H, 2-Ha), 2.80 (s, 3
H, 1a-H3), 2.95 (dd, J = 13.0, 6.0, 1 H, 2-Hb)
15.11 (q, C-6), 18.18 (s, C-4),
22.75 (d, C-7 or C-3), 23.17 (d, C-
3 or C-7), 28.19 (q, C-11), 28.56
(q, C-10), 29.64 (q, C-5), 37.90 (t,
C-8), 38.56 (q, C-1a), 50.07 (t, C-
2), 70.55 (s, C-9), 118.54 (s, C-1)
3615 (OH),
2215 (C∫N)
236 (8, M+), 221
(9), 178 (26),
177 (59), 163
(37), 139 (18),
123 (27), 109
(20), 96 (47), 91
(25), 81 (83), 59
(100)
0.80-1.00 (m, 2 H, 3-H and 7-H), 1.06 (s, 3 H, 6-
H3), 1.17 (s, 3 H, 5-H3), 1.23 (s, 3 H, 10-H3), 1.24
(s, 3 H, 11-H3), 1.48 (dd, J = 14.5, 7.0, 1 H, 8-Ha),
1.51 (dd, J = 14.5, 5.0, 1 H, 8-Hb), 2.95 (dd, J =
13.0, 8.5, 1 H, 2-Ha), 3.19 (dd, J = 13.0, 6.0, 1 H, 2-
Hb), 3.73 (ddt, J = 6.5, 1.5, 1.0, 2 H, 1a-H2), 5.39
(ddt, J = 10.0, 1.5, 1.0, 1 H, 3a-Ha), 5.42 (ddt, J =
17.0, 1.5, 1.0, 1 H, 3a-Hb), 5.93 (ddt, J = 17.0, 10.0,
6.5, 1 H, 2a-H)
15.69 (q, C-6), 19.36 (s, C-4),
24.42 (d, C-7 or C-3), 24.81 (d, C-
3 or C-7), 28.79 (q, C-11), 29.02
(q, C-10), 29.72 (q, C-5), 38.90 (t,
C-8), 49.46 (t, C-2), 55.16 (t, C-
1a), 71.28 (s, C-9), 119.19 (s, C-1),
120.16 (t, C-3a), 132.80 (d, C-2a)
Synthesis 2000, No. 8, 1148–1159 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Modification of the Tiemann Rearrangement
1157
Table 2 (continued)
Prod-
uct
IR (CHCl3)a
MS
m/z (%)
1H NMRb
d, J, W1/2 (Hz)
13C NMRb,c
d, J (Hz)
n (cm−1)
25e
3615 (OH),
2215 (C∫N),
1595 (C=C),
1480, 1370,
1030
322 (2, M+), 307
(7), 264 (14),
245 (22), 209
(10), 169 (12),
155 (10), 139
(14), 127 (100),
96 (22), 81 (36),
59 (47)
0.75-0.90 (m, 2 H, 3-H and 7-H), 0.91 (s, 3 H, 6-
H3), 1.06 (s, 3 H, 5-H3), 1.16 (s, 3 H, 10-H3), 1.17
(s, 3 H, 11-H3), 1.30 (dd, J = 14.5, 7.0, 1 H, 8-Ha),
1.42 (dd, J = 14.5, 5.0, 1 H, 8-Hb), 1.65 (br s, 1 H,
OH), 2.85 (dd, J = 13.0, 8.5, 1 H, 2-Ha), 3.03 (dd, J
= 13.0, 6.0, 1 H, 2-Hb), 4.24 (s, 2 H, 1a-H2), 6.8-
7.0 (m, 2 H, Ar-H), 7.2-7.4 (m, 1 H, Ar-H)
14.97 (q, C-6), 18.39 (s, C-4),
22.93 (d, C-7 or C-3), 23.07 (d, C-
3 or C-7), 28.35 (q, C-11), 28.54
(q, C-10), 29.53 (q, C-5), 37.78 (t,
C-8), 42.65 (t, C-1a), 48.21 (t, C-
2), 70.53 (s, C-9), 111.14 (d, 2JCF
=
25.3, C, C-4a), 111.40 (s, 2JCF
20.0, C-2a), 116.88 (s, C-1),
130.76 (d, 3JCF = 10.3, C-5a),
=
161.48 (s, 1JCF = 250.5, 3JCF = 7.3,
2 C, C-3a)
25f
26a
26c
3615 (OH),
2215 (C∫N),
1545 (C=C),
1360, 1120,
1030
376 (1, M+), 357
(1), 342 (2), 181
(40), 139 (42),
123 (29), 95
(25), 81 (45), 43
(100)
0.84-0.91 (m, 2 H, 3-H and 7-H), 0.99 (s, 3 H, 6-
H3), 1.11 (s, 3 H, 5-H3), 1.18 (s, 3 H, 10-H3), 1.23
(s, 3 H, 11-H3), 1.41 (dd, J = 13.5, 8.0, 1 H, 8-Ha),
1.48 (dd, J = 13.5, 6.0, 1 H, 8-Hb), 2.99 (dd, J =
13.5, 8.0, 1 H, 2-Hb), 3.21 (dd, J = 13.5, 6.0, 1 H,
2-Ha), 4.41 (s, 2 H, 1a-H2)
15.48 (q, C-6), 19.59 (s, C-4),
24.64 (d, C-3 or C-7), 24.65 (d, C-
7 or C-3), 28.74 (q, C-11), 28.92
(q, C-10), 29.68 (q, C-5), 38.83 (t,
C-8), 43.58 (t, C-1a), 50.16 (t, C-
2), 71.27 (s, C-9), 117.77 (s, C-1)
2220 (C∫N),
1720 (C=O),
1370, 1180
194 (4, M+), 179
(2), 139 (100),
81 (48), 69 (35),
43 (86)
1.30-1.80 (m, 2 H, 7-H2), 1.59 (s, 3 H, 6-H3), 2.02
(s, 3 H, 10-H3), 2.30 (m, 3 H, 3-H and 8-H2), 2.77
(s, 3 H, 1a-H3), 2.87 (m, 2 H, 2-H2), 4.75 (br s, 1
H, 5-Ha), 4.85 (br s, 1 H, 5-Hb)
17.89 (q, C-6), 23.35 (t, C-7),
29.72 (q, C-10), 38.58 (q, C-1a),
40.23 (t, C-8), 44.44 (d, C-30,
55.78 (t, C-2), 114.97 (t, C-5),
117.62 (s, C-1), 143.00 (s, C-
4),206.19 (s, C-9)
2220 (C∫N),
1715 (C=O),
1380, 920
270 (5, M+), 139
(77), 121 (14),
91 (100), 81
1.25-1.70 (m, 2 H, 7-H2), 1.48 (s, 3 H, 6-H3), 1.97
(s, 3 H, 10-C3), 2.22 (t, J = 7.5, 2 H, 8-H2), 2.30
(m, 1 H, 3-H), 2.77 (d, J = 7.5, 2 H, 2-H2), 4.04 (s,
2 H, 1a-H2), 4.71 (br s, 1 H, 5-Ha), 4.81 (br s, 1 H,
5-Hb), ª7.22 (br s, 5 H, Ar-H)
17.66 (q, C-6), 23.15 (t, C-7),
29.49 (q, C-10), 40.04 (t, C-8),
44.19 (d, C-3), 52.63 (t, C-2),
55.18 (t, C-1a), 114.73 (t, C-5),
116.97 (s, C-1), 128.14 (d, 2 C, C-
3a or C-4a), 128.15 (d, C-5a),
128.41 (d, 2 C, C-4a or C-3a),
134.34 (s, C-2a), 142.72 (s, C-4),
206.14 (s, C-9)
(16), 43 (66)
27a
2215 (C∫N),
1720 (C=O),
1640 (C=C)
262 (33, M+),
247 (46), 219
(64), 205 (74),
201 (87), 187
(39), 173 (64),
159 (100), 145
(54), 133 (87)
0.99 (s, 6 H, 9-H3 and 10-H3), 1.37 (t, J = 10.5, 1 H,
7-Ha), 1.60 (m, 2 H),1.80 (m, 2 H), 2.04 (s, 3 H, 15-
H3), 2.20-2.35 (m, 5 H), 2.80 (s, 3 H, 1a-H3), 3.00
(t, J = 8.0, 2 H, 2-H2), 4.72 (br s, 1 H, 5-Ha), 4.81
(br s, 1 H, 5-Hb)
22.10 (q, C-9), 24.31 (t, C-12),
29.62 (q, C-15), 30.87 (q, C-10),
32.00 (t, C-3), 33.47 (s, C-8),
38.66 (q, C-1a), 39.66 (t, C-7),
41.18 (d, C-6), 41.64 (t, C-13),
47.70 (d, C-11), 51.41 (t, C-2),
109.38 (t, C-5), 118.02 (s, C-1),
147.96 (s, C-4), 208.17 (s, C-14)
27c
2220 (C∫N),
1715 (C=O),
1640 (C=C)
338 (63, M+),
323 (34), 295
(57), 281 (69),
267 (37), 225
(51), 213 (97),
149 (100), 134
(29), 121 (66)
0.97 (s, 3 H, 9-H3 or 10-H3), 0.98 (s, 3 H, 10-H3 or
9-H3), 1.42 (t, J = 10.5, 1 H, 7-Ha), 1.50-1.80 (m, 4
H), 2.05 (s, 3 H, 15-H3), 2.20-2.35 (m, 5 H), 2.97
(t, J = 8.0, 2 H, 2-H2), 4.14 (s, 2 H, 1a-H2), 4.69 (br
s, 1 H, 5-Ha), 4.79 (br s, 1 H, 5-Hb), 7.31 (m, 5 H,
Ar-H)
22.03 (q, C-9), 24.24 (t, C-12),
29.61 (q, C-15), 30.80 (q, C-10),
32.11 (t, C-3), 33.39 (s, C-8),
39.44 (t, C-7), 41.05 (d, C-6),
41.61 (t, C-13), 47.58 (d, C-11),
48.74 (t, C-2), 55.65 (t, C-1a),
109.37 (t, C-5), 118.19 (s, C-1),
128.18 (d, 2 C, C-3a or C-4a),
128.30 (d, C-5a), 128.64 (d, 2 C,
C-4a or C-3a), 134.52 (s, C-2a),
147.83 (s, C-4), 208.23 (s, C-14)
28a
2300-3300
(N+-H), 1580
(C-N+)
167 (1, M+ -
1.01 (s, 3 H, 5-H3), 1.13 (s, 3 H, 4-H3), 1.13 (m, 1
H, 2-H), 1.45 (dd, J = 8.0, 8.0, 1 H, 6-H), 1.64 (d,
J = 1.5, 3 H, 9-H3), 1.68 (d, J = 1.5, 3 H, 10-H3),
2.60 (s, 3 H, 1a-H3), 2.88 (dd, J = 13.0, 8.0, 1 H,
1-Ha), 2.94 (dd, J = 13.0, 6.5, 1 H, 1-Hb), 4.74
(dqq, J = 8.0, 1.5, 1.5, 1 H, 7-H), 9.45 (br s, 2 H,
+NH2)
15.28 (q, C-5), 18.43 (q, C-9),
20.32 (s, C-3), 23.72 (d, C-2),
25.56 (q, C-10), 25.83 (d, C-6),
27.93 (q, C-4), 31.54 (q, C-1a),
45.67 (t, C-1), 117.39 (d, C-7),
136.72 (s, C-8)
HCl), 152 (2),
98 (5), 95 (5),
93 (3), 81 (3),
72 (26), 67 (3),
44 (100), 36 (9)
Synthesis 2000, No. 8, 1148–1159 ISSN 0039-7881 © Thieme Stuttgart · New York

1158
S. A. Bakunov et al.
PAPER
Table 2 (continued)
Prod-
uct
IR (CHCl3)a
MS
m/z (%)
1H NMRb
d, J, W1/2 (Hz)
13C NMRb,c
d, J (Hz)
n (cm−1)
28c
2300-3300
(N+-H), 1580
(C-N+)
218 (1), 200 (1),
174 (3), 152 (2),
148 (19), 120
(42), 95 (5), 91
(100)
0.86 (s, 3 H, 5-H3), 1.07 (s, 3 H, 4-H3), 1.38 (m, 1
H, 2-H), 1.35 (t, J = 8.5, 1 H, 6-H), 1.58 (br s, 6 H,
9-H3 and 10-H3), 2.75 (m, 2 H, 1-H2), 3.93 (AB-
system: JAB = 14.0, DdAB = 12, 2 H, 1a-H2), 4.57
(dqq, J = 8.0, 1.5, 1.5, 1 H, 7-H), 7.20-7.60 (m, 5
H, Ar-H), 9.80 (br s, 2 H, +NH2)
14.95 (q, C-5), 18.33 (q, C-9),
20.44 (s, C-3), 23.85 (d, C-6),
25.45 (q, C-10), 25.83 (d, C-6),
27.86 (q, C-4), 43.01 (t, C-1),
49.61 (t, C-1a), 117.34 (d, C-7),
128.74 (d, 2 C, C-4a), 128.96 (d,
C-5a), 129.88 (d, C-3a), 130.49 (s,
C-2a), 136.41 (s, C-8)
28g
2300-3300
(N+-H), 1580
(C-N+),
335 (1), 320 (1),
266 (4), 240
0.91 (s, 3 H, 5-H3), 1.10 (s, 3 H, 4-H3), 1.25 (m, 1
H, 2-H), 1.42 (dd, J = 8.5, 8.0, 1 H, 6-H), 1.62 (br
s, 3 H, 9-H3 or 10-H3), 1.63 (br s, 3 H, 10-H3 or 9-
15.00 (q, C-5), 18.38 (q, C-9),
20.48 (s, C-3), 23.83 (d, C-2),
25.50 (q, C-10), 25.84 (d, C-6),
27.87 (q, C-4), 43.09 (t, C-1),
49.30 (t, C-1a), 117.34 (d, C-7),
118.92 (d, 2 C, C-9a), 120.23 (d,
C-7a), 123.46 (d, C-3a or C-11a),
124.46 (d, C-11a or C- 3a), 129.62
(d, 2 C, C-10a), 130.30 (d, C-4a),
132.39 (s, C-2a), 136.54 (s, C-8),
156.36 (s, C-6a), 157.47 (s, C-8a)
(45), 212 (27),
200 (4), 198 (4),
183 (100), 171
(5), 169 (5), 168
(4), 152 (7)
1575, 1485
H3), 2.80 (m, 2 H, 1-H2), 3.98 (AB-system: JAB =
14.0, DdAB = 10, 2 H, 1a-H2), 4.72 (dqq, J = 8.0,
1.5, 1.5, 1 H, 7-H), 6.85-7.50 (m, 9 H, Ar-H), 9.90
(br s, 2 H, +NH2)
a The NMR spectra were recorded for solutions in the following solvents: CDCl3 for compounds 9, 11, 12, 15, 20a, 20b, 20c, 20d, 22a,
22c, 23a, 23b, 23c, 23e, 23f, 24e, 25a, 25e, 27a, 27c, 28a, 28c, 28g), CDCl3:CCl4= 1:1 v/v for compounds 19b, 19c, 24a, 24c, 26a,
26c), CD3OD for compounds 14, 18a, 18b, 18c, 19a, 21a, 21b, 21c, 22b, 24b, 24f, 25b, 25f). Signal assignments are given in accordance
with the numbering shown in Schemes 2, 4 and 6.
b 19F NMR spectra were recorded for the following fluorine containing compounds. 23e: d = 47.90; 23f: d = 1.44 (2 F, 4a-F2), 10.27 (1 F, 5a-
F), 20.33 (2 F, 3a-F2); 24e: d = 48.10; 24f: d = 0.95 (2 F, 4a-F2), 9.48 (5a-F), 21.29 (2F, 3a-F2); 25e: d = 48.37; 25f: d = 0.75 (2 F, 4a-F2), 9.08
(5a-F), 21.89 (2 F, 3a-F2).
c Multiplicity of the carbon resonances are given in accordance with the off-resonance proton-decoupled spectra. For the 2,6
difluorobenzyl derivatives 23e, 24e and 25e values of JC-F couplings are given in brackets. In the spectra of pentafluorobenzyl derivatives
23f, 24f and 25f chemical shifts of the aromatic carbons were not determined because of their low intensities due to plural carbon-fluorine
couplings.
Acknowledgement
amide (25b), (2,6-difluorobenzyl)[(1R,3S)-3-(2-hydroxy-2-methyl-
propyl)-2,2-dimethylcyclopropylmethyl]cyanamide (25e),
The authors thank Russian Foundation for Basic Research (Grant
96-15-97017) for the financial support of this work.
[(1R,3S)-3-(2-hydroxy-2-methylpropyl)-2,2-dimethylcyclopropyl-
methyl]pentafluorophenylmethylcyanamide (25f), [(1R,3S)-3-(2-
hydroxy-2-methylpropyl)-2,2-dimethylcyclopropylmethyl]-(3-
phenoxybenzyl)cyanamide (25g, yield 74%, described earlier17),
( )-methyl[3-methyl-2-(3-oxobutyl)but-3-enyl]cyanamide (26a),
( )-benzyl[3-methyl-2-(3-oxobutyl)but-3-enyl]cyanamide (26c),
{3-[(1S,2R)-3,3-dimethyl-2-(3-oxobutyl)cyclobutyl]but-3-enyl}-
methylcyanamide (27a), benzyl{3-[(1S,2R)-3,3-dimethyl-2-(3-
oxobutyl)cyclobutyl]but-3-enyl}cyanamide (27c) (Tables 1 and 2).
References
#
Present address: Chemistry department, University of Idaho,
Moscow, Idaho, USA
Present address: Department of chemistry, University of
†
Oregon, Oregon, USA
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Synthesis 2000, No. 8, 1148–1159 ISSN 0039-7881 © Thieme Stuttgart · New York