Transformation of esters into 2-substituted allyl halides via tertiary cyclopropanols: Application in the stereoselective synthesis of (2S,3S,7S)-3,7-dimethyl-2-pentadecyl acetate, the sex pheromone of the pine sawfly Neodiprion sertifer

Article abstract of DOI:10.1002/ejoc.200600481

(2S,3S,7S)-3,7-Dimethyl-2-pentadecyl acetate (ac-1), the sex pheromone of the pine sawfly Neodiprion sertifer, has been newly synthesized by the transformation of the corresponding esters 8 and 12 into 2-oxyalkyl-substituted allyl bromides 4 and 5 via ter

Full text of DOI:10.1002/ejoc.200600481

FULL PAPER
DOI: 10.1002/ejoc.200600481
Transformation of Esters into 2-Substituted Allyl Halides via Tertiary
Cyclopropanols: Application in the Stereoselective Synthesis of
(2S,3S,7S)-3,7-Dimethyl-2-pentadecyl Acetate, the Sex Pheromone of the Pine
Sawfly Neodiprion sertifer
Andrei V. Bekish,[a] Konstantin N. Prokhorevich,[a] and Oleg G. Kulinkovich*[a]
Keywords: Asymmetric synthesis / Pheromones / Lactic acid / Cyclopropanols
(2S,3S,7S)-3,7-Dimethyl-2-pentadecyl acetate (ac-1), the sex
pheromone of the pine sawfly Neodiprion sertifer, has been
newly synthesized by the transformation of the correspond-
ing esters 8 and 12 into 2-oxyalkyl-substituted allyl bromides
4 and 5 via tertiary cyclopropanols 6 and 7.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
viously, we applied this methodology to the nonstereoselec-
tive construction of the methyl-branched skeleton of 3,7-
dimethyl-2-tridecyl acetate and propionate,[7] the sex at-
tractants of the pine sawfly Diprion pini,[8] and also to the
stereoselective synthesis of the alkaloid (–)-heliotridane.[9]
Introduction
Stereogenic methyl branches of carbon skeletons are
characteristic structural elements of the pheromones of
many insect species and their stereochemical configuration
often exerts significant influence on their attractiveness.[1]
One such substance is (2S,3S,7S)-3,7-dimethylpentadecan-
2-ol (diprionol) (1), the acetate (ac-1) of which is the major
component of the pine sawfly Neodiprion sertifer phero-
mone.[2] It has been established that pest attraction to the
synthetic pheromone (2S,3S,7S)-ac-1 is significantly re-
duced if the isomeric impurity content of (2S,3R,7R)-ac-1
is more than 3%.[3] The stereoselective synthesis of com-
pound 1 and its acylates has been described in several pa-
pers.[3–5] Alkylation reactions of chiral oxiranes,[3,4a,b,f] alkyl
sulfonates,[4e,f,h] β-hydroxy acid esters,[4h] derivatives of alk-
anoic acids with oxazoline or prolinol chiral auxiliaries,[3,4c]
as well as Claisen rearrangement of allyl vinyl ethers[4f] have
been used in the creation of chiral centres at the C-3 and
C-7 positions of this molecule. Resolution of diastereomeric
mixtures of α-methyl-substituted secondary alcohols by cry-
stallization[4d,4g] and functional group manipulations of
(R)-citronellic acid[4a,b,d,g] are other methods that have also
been used to create chiral centres at the C-3 and C-7 posi-
tions, respectively.
Results and Discussion
The key chiral building blocks 2 and 3 were synthesized
from 2-oxyalkyl-substituted allyl halides 4 and 5, which in
turn were prepared starting from the readily accessible hy-
droxycyclopropane precursors 6 and 7 (Scheme 1).
THP-protected ethyl (S)-lactate (8) was transformed into
bromide 4 by titanium-catalyzed cyclopropanation of the
ethoxycarbonyl group with ethylmagnesium bromide[10,11]
and subsequent cationic cyclopropyl–allyl isomerization[6]
of the methanesulfonate of the 1-substituted cyclopropanol
6 (Scheme 2).[7,12] Replacement of the bromine atom in
compound 4 with an ethoxycarbonyl group upon treatment
with zinc powder, activated by copper(I) chloride in the
presence of ethyl chloroformate, resulted in the smooth for-
mation of ester 9. The latter, without further purification,
was deprotected under acidic conditions to give, after con-
comitant lactonization, compound 10.[13] The carbon–car-
bon double bond in lactone 10 was shifted under the action
of triethylamine to form α,β-unsaturated lactone 11, iso-
lated by column chromatography on silica gel in 42% yield
based on THP-protected ethyl (S)-lactate (8).[14]
In this work, we report on the stereoselective synthesis
of (2S,3S,7S)-3,7-dimethylpentadecan-2-ol (1) based on the
creation of methyl branches in the carbon chain using the
transformation of carboxylic esters into 2-substituted allyl
halides via sulfonates of tertiary cyclopropanols.[6] Pre-
The preferential formation of (3S,4S)-butanolide 2 was
observed upon treatment of unsaturated lactone 11 with so-
dium borohydride in the presence of nickel chloride.[7,16]
The diastereoselectivity of the reaction was unsatisfactory
(cis-2/trans-2 = 3–4:1) when methanol or ethanol was used
as the solvent. However, it was substantially enhanced (cis-
[a] Department of Organic Chemistry, Belarusian State University,
Nezavisimosty Av. 4, 220030 Minsk, Belarus
Fax: +375-17-2265609
E-mail: kulinkovich@bsu.by
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FULL PAPER
Scheme 1. Retrosynthetic analysis of 1 and ac-1.
rivative obtained with magnesium bromide[6] led to bromide
5 in high yield. The latter was transformed, in a moderate
yield, into α-methylene aldehyde 13 by Kornblum oxi-
dation,[21] and then into the diethyl acetal 14 by a standard
procedure. Biohydrogenation of the methylene moiety in
compound 14 with baker’s yeast led to chiral (S)-alcohol
3, whose enantiomeric purity, as determined by Mosher’s
method, was more than 97%.[22] Alcohol 3 was converted
into bromide 15 and then into sulfone 16 by standard pro-
cedures. Alkylation of sulfone 16 gave compound 17, subse-
Scheme 2. Synthesis of lactone 2. Reagents and conditions: (a) DHP,
PPTS, CH2Cl2, reflux; (b) EtMgBr, Ti(OiPr)4, Et2O/THF; (c) MsCl,
Et3N, Et2O; (d) MgBr2, Et2O/CHCl3, reflux; (e) Zn, CuCl, 1,2-dibro-
moethane, ClCO2Et, reflux; (f) MeOH, THF, HCl, reflux; (g) Et3N,
reflux; (h) NaBH4, NiCl2, B(OH)3, H2O.
2/trans-2 = 10:1) by carrying out the reduction in an aque-
ous medium. In this case, however, the reaction proceeded
at a significantly lower rate, requiring more than 12 h for
completion. We have found that lactone 11 could be re-
duced by this nickel reagent much faster in the presence of
boric acid,[17] and the reaction was complete after 1 h with-
out a reduction of the diastereoselectivity.
To synthesize the chiral building block 3 we used baker’s
yeast mediated biohydrogenation of the methylene-substi-
tuted acetal 14 as the key step.[18] The latter was readily
obtained from ethyl (benzyloxy)acetate (12)[19] by reaction
with ethylmagnesium bromide in the presence of titani-
um(IV) isopropoxide[20] to form cyclopropanol 7. Mesyl-
Scheme 3. Synthesis of bromide 20. Reagents and conditions: (a)
EtMgBr, Ti(OiPr)4; (b) MsCl, Et3N; (c) MgBr2; (d) DMSO,
NaHCO3; (e) HC(OEt)3, H+; (f) baker’s yeast; (g) Bu4NBr; (h)
ation of compound 7 and subsequent treatment of the de- Bu4NPhSO2; (i) 1. BuLi; 2. C7H15I; (j) Na/Hg, EtOH; (k) H2, Pd/C.
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Transformation of Esters into 2-Substituted Allyl Halides
FULL PAPER
Scheme 4. Synthesis of 1 and ac-1. Reagents and conditions: (a) morpholine, 100 °C, 24 h; (b) recrystallization from diethyl ether; (c)
DHP, PPTS, CH2Cl2; (d) (2R)-2-methyldecyllithium, Et2O/THF, –78 °C; (e) N2H4, KOH, triethylene glycol, 180–210 °C; (f) MeOH,
PPTS, reflux; (g) CH3COCl, Et3N, Et2O.
quent reduction of which with sodium amalgam led to ether
Experimental Section
18. Catalytic debenzylation of the latter and replacement of
General: Melting points were determined with a capillary appara-
the hydroxy group in alcohol 19[23] by a bromine atom gave
tus. Optical rotations were measured at 20 2 °C with a CM-3 po-
bromide 20 (Scheme 3),[23c] which was then used in the
larimeter (scale factor: 0.05°). Column chromatography was per-
preparation of (2R)-2-methyldecyllithium. Use of this lith-
formed on Merck 60 silica gel (70–230 mesh). IR spectra were re-
corded with a Specord IR-75 or Vertex 70 spectrometer. 1H and
13C NMR spectra were obtained with a Bruker AC 400 instrument
ium compound in a coupling reaction with lactone 2 [ob-
tained by a multistep synthesis from (2R,3R)-tartaric acid
in an overall yield of less than 30%[3,4c]] followed by at 400 and 100 MHz, respectively, in CDCl3 (TMS at δ = 0.00 ppm
or CHCl3 at δ = 7.26 ppm for 1H NMR and CHCl3 at δ = 77.0 ppm
Kishner–Wolff reduction of the carbonyl group in the re-
for 13C NMR as internal standard).
sulting product to form the target alcohol (2S,3S,7S)-1 has
been reported previously.[3,4c]
Ethyl
3-[(1S)-1-(Tetrahydro-2H-pyran-2-yloxy)ethyl]but-3-enoate
At the same time, lactone 2 was formed as a mixture of
cis/trans isomers in a ratio of 10:1 and additional purifica-
tion was required for the preparation of alcohol 1. Since
column chromatography was ineffective for this purpose, we
transformed the crude lactone 2 into a crystalline morph-
oline 21, single recrystallization of which from diethyl ether
resulted in a de and ee of more than 98%. Tetrahydropy-
ranylation of the hydroxy group in compound 21 and reac-
tion of the resulting amide 22 with (2R)-2-methyldecylli-
thium (obtained from bromide 20) gave ketone 23.
Kishner–Wolff reduction of the carbonyl group in 23[3,4c]
and removal of the THP protecting group led to the target
(2S,3S,7S)-3,7-dimethylpentadecan-2-ol (1), which was then
transformed into the acetate ac-1[24] containing less than
3% isomeric compounds as impurities (Scheme 4).
(9): A vigorously stirred suspension of zinc powder (4.80 g,
73.4 mmol) and CuCl (0.30 g, 3.0 mmol) in THF (8 mL) was re-
fluxed for 30 min under argon. Ethyl chloroformate (3.5 mL,
37 mmol) was added in one portion to the resulting mixture. Then
a solution of allyl bromide 4[7] (3.70 g, 14.9 mmol) and 1,2-dibro-
moethane (0.15 g, 0.80 mmol) in a mixture of THF (7 mL) and
diethyl ether (7 mL) was added dropwise over 30 min to the stirred
reaction mixture upon refluxing. The stirred reaction mixture was
refluxed for an additional 30 min, cooled to room temperature and
quenched with a saturated solution of NaHCO3 (10 mL). The reac-
tion mixture was filtered and the inorganic precipitate was ad-
ditionally washed with diethyl ether (4×10 mL). The aqueous
phase was separated and extracted with diethyl ether (4×5 mL).
The combined organic phases were washed with a saturated
NaHCO3 solution, brine and dried with Na2SO4. Removal of the
solvent under reduced pressure led to ester 9 (3.65 g), which was
used in the next step without further purification. IR (CCl ): ν =
˜
4
3090, 1740, 1640 cm–1. 1H NMR (400 MHz, CDCl3): δ = 1.23–1.31
(m,
6 H, OCH2CH3 and CH3CH), 1.44–1.90 (m, 6 H,
Conclusions
CH2CH2CH2), 2.96–3.23 (m, 2 H, 2-H), 3.37–3.54 (m, 1 H,
OCH2CH2), 3.78–3.95 (m, 1 H, OCH2CH2), 4.13 (q, J = 7.3 Hz, 1
H, OCH2CH3), 4.14 (q, J = 7.3 Hz, 1 H, OCH2CH3), 4.28–4.38
(m, 1 H, CH3CH), 4.52–4.60 (m, 0.5 H, OCHO), 4.69–4.76 (m, 0.5
H, OCHO), 5.02–5.04 (m, 0.5 H, 4-H), 5.06–5.08 (m, 0.5 H, 4-H),
5.16–5.19 (m, 0.5 H, 4-H), 5.22–5.24 (m, 0.5 H, 4-H) ppm.
C13H22O4 (242.3): calcd. C 64.44, H 9.15; found C 64.59, H 9.23.
Acetate ac-1, the sex pheromone of the pine sawfly Neo-
diprion sertifer, was prepared in a stereoisomerically pure
form in a total yield of 15%, starting from the THP-pro-
tected ethyl (S)-lactate 8. For the stereospecific formation
of the methyl branches at the C-3 and C-7 positions of com-
pound 1, the carbon–carbon double bonds in unsaturated
lactone 11 and the acetal of α-methylene aldehyde 14 were
reduced.
(5S)-4,5-Dimethylfuran-2(5H)-one (11): Concentrated aqueous HCl
(4 drops) and MeOH (1.14 mL, 28.2 mmol) were added to a solution
of ester 9 (3.65 g) in THF (20 mL). The reaction mixture was re-
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A. V. Bekish, K. N. Prokhorevich, O. G. Kulinkovich
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fluxed for 40 min under argon. Then Et3N (1.05 mL, 7.53 mmol)
was added and boiling was continued for an additional 1 h. The
portion was purified by chromatography on silica gel (eluent: from
petroleum ether to petroleum ether/ethyl acetate, 5:1) to give 1-
greater part of the solvent was carefully removed at atmospheric [(benzyloxy)methyl]cyclopropyl methanesulfonate as a colourless
pressure and the residue was diluted with diethyl ether (25 mL) and
brine (40 mL). The organic layer was separated, and the aqueous
layer was extracted with diethyl ether (6×15 mL). The combined
organic extracts were dried with Na2SO4 and carefully concentrated.
The residue was purified by chromatography on silica gel (eluent:
light petroleum ether/diethyl ether, 3:1) to give lactone 11 (1.23 g,
oil. IR (CCl ): ν = 3093 cm–1. 1H NMR (400 MHz, CDCl3): δ =
˜
4
0.86 (dd, J = 7.8, 6.7 Hz, 2 H, 2-H, 3-H), 1.36 (t, J = 7.3 Hz, 2 H,
2-H, 3-H), 3.02 (s, 3 H, CH3SO3); 3.76 [s, 2 H, O-CH2-C(OMs)],
4.61 (s, 2 H, PhCH2), 7.27–7.37 (m, 5 H, C6H5) ppm. 13C NMR
(CDCl3): δ = 10.6, 39.6, 64.5, 72.8, 72.9, 127.7, 127.8, 128.4,
137.5 ppm. C12H16O4S (256.3): calcd. C 56.23, H 6.29; found C
74% based on bromide 4) as a colourless oil. [α]D = +20.2 (c = 56.30, H 6.23.
5.00, CH Cl ). IR (CCl ): ν = 1775, 1645 cm–1. 1H NMR (400 MHz,
˜
2
2
4
A solution of MgBr2 prepared from magnesium (14.6 g, 600 mmol)
and 1,2-dibromethane (112.8 g, 600 mmol) in diethyl ether
(300 mL) was added to a stirred and refluxed solution of 1-[(ben-
zyloxy)methyl]cyclopropyl methanesulfonate (52.22 g, 204 mmol)
in diethyl ether (150 mL). The reaction mixture was then refluxed
for 2 days and then quenched with water (200 mL). The organic
layer was separated and the aqueous layer extracted with diethyl
ether (3×100 mL). The combined organic extracts were washed
with brine, dried with MgSO4 and concentrated under reduced
pressure. Compound 5 (45.30 g, 92%) was isolated by column
chromatography on silica gel (eluent: from petroleum ether to pe-
troleum ether/ethyl acetate, 5:1) as a colourless oil. The spectral
data were similar to those reported in the literature.[26]
CDCl3): δ = 1.39 (d, J = 6.8 Hz, 3 H, 5-Me), 2.02 (d, J = 1.2 Hz, 3
H, 4-Me), 4.86 (m, 1 H, 5-H), 5.73 (m, 1 H, 3-H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 13.5, 17.9, 80.8, 116.1, 169.8, 172.9 ppm.
C6H8O2 (112.1): calcd. C 64.27, H 7.19; found C 64.35, H 7.13.
(4S,5S)-4,5-Dimethyldihydrofuran-2(3H)-one (2): NaBH4 (3.50 g,
92.5 mmol) and then B(OH)3 (4.85 g, 78.4 mmol) were added at
0 °C in small portions over 5 min each to a stirred and cooled emul-
sion of 11 (1.20 g, 10.7 mmol) in aqueous NiCl2 (0.2 , 55 mL).
The reaction mixture was stirred at 0 °C for an additional 1 h, then
saturated with NaCl at room temperature and extracted with di-
ethyl ether (4×30 mL). The combined organic fractions were dried
with Na2SO4 and carefully concentrated. The lactone 2 (cis/trans =
10:1, 1.20 g, 98%) obtained was used in the next step without fur-
ther purification. The trans-isomer content was determined from
the 1H NMR spectrum of the reaction mixture on the basis of
integral intensities of signals of methyl protons using data pub-
lished in the literature for individual cis and trans isomeric lactones
2.[25] [α]D = –35.5 (c = 6.67, Et2O). The spectral data were similar
to those reported in the literature.[25]
2-[(Benzyloxy)methyl]acrylaldehyde (13): A solution of allyl bro-
mide 5 (32.0 g, 132.7 mmol) and NaHCO3 (33.6 g, 400 mmol) in
dry DMSO (250 mL) was stirred at room temperature for 48 h with
regular removal of the resulting CO2 and Me2S in a 10 mbar vac-
uum. After completion of the reaction, the mixture was diluted
with water (800 mL) and extracted with petroleum ether
(5×400 mL). Removal of the solvent under reduced pressure and
column chromatography of the residue on silica gel (eluent: from
petroleum ether to petroleum ether/ethyl acetate, 5:1) gave aldehyde
13 (11.71 g, 50%). The spectral data were similar to those reported
in the literature.[27]
1-[(Benzyloxy)methyl]cyclopropanol (7): A solution of ethylmagne-
sium bromide obtained from magnesium (32.81 g, 1350 mmol) and
ethyl bromide (152.6 g, 1400 mmol) in diethyl ether (550 mL) was
slowly added dropwise with stirring and reflux to a solution of
ethyl (benzyloxy)acetate (58.2 g, 300 mmol) and titanium tetraisop-
ropoxide (85.2 g, 300 mmol) in diethyl ether (130 mL) and benzene
(200 mL). At the end of the addition the reaction mixture was co-
oled and added through a dropping funnel with stirring and cool-
ing to sulfuric acid (750 mL, 25% aqueous solution) at such a speed
that the temperature did not exceed 10 °C. The aqueous phase was
separated and extracted with diethyl ether (3×100 mL). The com-
bined organic phases were washed with a saturated NaHCO3 solu-
tion, brine, dried with MgSO4 and concentrated under reduced
pressure. Column chromatography on silica gel (eluent: from petro-
leum ether to petroleum ether/ethyl acetate, 5:1) gave compound 7
[2-(Diethoxymethyl)allyloxymethyl]benzene (14): A solution of alde-
hyde 13 (11.1 g, 63.2 mmol), triethyl orthoformate (9.62 g,
65 mmol) and NH4NO3 (0.1 g) in dry ethanol (10 mL) was stirred
at 50 °C for 8 h. Removal of the solvent under reduced pressure
and column chromatography of the residue on silica gel (eluent:
from petroleum ether to petroleum ether/ethyl acetate, 5:1) gave
acetal 14 (13.3 g, 84%). IR (CCl ): ν = 1453 cm–1. 1H NMR
˜
4
(400 MHz, CDCl3): δ = 1.22 (t, J = 7.2 Hz, 6 H, CH3), 3.49 (dq, J
= 9.3, 7.2 Hz, 2 H, OCH2Me), 3.62 (dq, J = 9.3, 7.2 Hz, 2 H,
OCH2Me), 4.09 (s, 2 H, 1Ј-H), 4.55 (s, 2 H, PhCH2), 4.91 [s, 1 H,
CH(OEt)2], 5.36–5.38 (m, 1 H, 3Ј-H), 5.38–5.41 (m, 1 H, 3Ј-H),
7.26–7.39 (m, 5 H, C6H5) ppm. 13C NMR (CDCl3): δ = 15.1, 61.7,
69.3, 72.3, 101.4, 114.2, 127.4, 127.5, 128.3, 138.3, 142.9 ppm.
C15H22O3 (250.3): calcd. C 71.97, H 8.86; found C 71.95, H 8.83.
(41.7 g, 78%) as a colourless oil. IR (CCl ): ν = 3593, 3453,
˜
4
3093 cm–1. 1H NMR (400 MHz, CDCl3): δ = 0.55 (dd, J = 6.8,
5.6 Hz, 2 H, 2-H, 3-H), 0.83 (dd, J = 6.8, 5.6 Hz, 2 H, 2-H, 3-H),
2.94–3.00 (br. s, 1 H, OH), 3.52 [s, 2 H, O-CH2-C(OH)], 4.60 (s, 2
H, PhCH2O), 7.26–7.39 (m, 5 H, C6H5) ppm. 13C NMR (CDCl3):
δ = 11.6, 54.5, 72.9, 76.0, 127.6, 127.7, 128.3, 137.9 ppm. C11H14O2
(178.2): calcd. C 74.13, H 7.92; found C 74.20, H 7.95.
(2S)-3-Benzyloxy-2-methylpropan-1-ol (3): A known method for
baker’s yeast mediated reduction[18] was modified and adapted for
the preparative-scale synthesis of compound 3. A solution of acetal
14 (12.00 g, 48.0 mmol) in ethanol (60 mL) was added portionwise
(in six portions over a period of 3 d) with stirring and at an internal
temperature 34–38 °C to a suspension of pressed baker’s yeast
(1200 g) in a buffer solution (pH5.25) of citric acid monohydrate
(26.88 g, 128 mmol) and K2CO3 (15.46 g, 112 mmol) in water (2.4 L).
For these 3 days and for a day afterwards, the reaction mixture was
stirred and a sugar (3–6 g, 10–12 times a day) was added. Then the
yeast suspension was carefully extracted with petroleum ether
(6×2 L), dried with Na2SO4 and concentrated under reduced pres-
sure. Column chromatography on silica gel (eluent: from petroleum
ether to petroleum ether/ethyl acetate, 5:1) gave the title compound
[2-(Bromomethyl)prop-2-en-1-yloxy]methylbenzene (5): Methanesul-
fonyl chloride (30.93 g, 270 mmol) was added dropwise with stir-
ring at 0 °C to a solution of cyclopropanol 7 (39.0 g, 219 mmol)
and triethylamine (45.5 g, 450 mmol) in diethyl ether (500 mL). The
reaction mixture was kept at room temperature overnight and then
treated with water (150 mL). The aqueous phase was extracted with
diethyl ether (3×150 mL). The combined organic phases were
washed with brine (100 mL), dried with MgSO4 and concentrated
under reduced pressure to give 1-[(benzyloxy)methyl]cyclopropyl
methanesulfonate (55.44 g, 99%). For analytical purposes, a small
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Transformation of Esters into 2-Substituted Allyl Halides
FULL PAPER
(3.60 g, 42%) as a colourless oil. Enantiomeric excess of the alcohol 2.30–2.42 (m, 0.5 H, 2-H), 2.49–2.59 (m, 0.5 H, 2-H), 3.18–3.28
3 (ee Ͼ 97%) was determined by Mosher’s method.[22] The spectral (m, 1.5 H, 1-H, 3-H), 3.31–3.37 (m, 0.5 H, 3-H), 3.47 (dd, J = 9.2,
data were similar to those reported in the literature.[28]
6.7 Hz, 0.5 H, 1-H), 3.82 (dd, J = 9.2, 7.2 Hz, 0.5 H, 1-H), 4.29 (d,
J = 11.9 Hz, 0.5 H, PhCH2), 4.37 (d, J = 11.9 Hz, 0.5 H, PhCH2),
4.47 (s, 0.5 H, PhCH2), 4.48 (s, 0.5 H, PhCH2), 7.16–7.34 (m, 5
H, C6H5CH2), 7.44–7.51 (m, 2 H, C6H5SO2), 7.54–7.61 (m, 1 H,
C6H5SO2), 7.81 (d, J = 6.9 Hz, 1 H, C6H5SO2), 7.86 (d, J = 7.1 Hz,
1 H, C6H5SO2) ppm. 13C NMR (CDCl3): δ = 11.2, 13.85, 13.90,
13.95, 22.35, 22.40, 23.1, 26.1, 27.3, 28.6, 28.7, 28.8, 29.3, 31.45,
31.50, 31.6, 31.8, 34.1, 63.9, 65.1, 72.4, 72.5, 72.9, 127.25, 127.35,
127.40, 127.5, 128.1, 128.2, 128.4, 128.85, 128.90, 129.1, 133.2,
137.9, 138.4, 139.2, 139.9 ppm. C24H34O3S (402.6): calcd. C 71.60,
H 8.51; found C 71.45, H 8.51.
(2R)-3-Bromo-2-[(methylpropyloxy)methyl]benzene (15): A solution of
methanesulfonyl chloride (2.06 g, 18 mmol) in diethyl ether (15 mL)
was added dropwise at 0 °C to a stirred solution of alcohol 3 (2.70 g,
15.0 mmol) and triethylamine (2.42 g, 24 mmol) in diethyl ether
(50 mL). The reaction mixture was slowly warmed to room tempera-
ture and quenched with water (30 mL). The aqueous phase was ex-
tracted with diethyl ether (2×20 mL). The combined organic phases
were washed with brine (20 mL), dried with MgSO4 and concentrated
under reduced pressure to give (2R)-3-benzyloxy-2-methylpropyl
1
methanesulfonate (3.74 g, 97%). [α]D = –8.9 (c = 5.00, MeOH). H
NMR (400 MHz, CDCl3): δ = 1.03 (d, J = 7.1 Hz, 3 H, 2-Me), 2.21
(m, 1 H, 2-H), 2.96 (s, 3 H, CH3SO3), 3.39 (dd, J = 9.2, 6.9 Hz, 1
H, 3-H), 3.45 (dd, J = 9.2, 5.1 Hz, 1 H, 3-H), 4.19 (dd, J = 9.6,
(2S)-2-[(Methyldecyloxy)methyl]benzene (18): Powdered 3% sodium
amalgam (57.5 g, 75.0 mmol) was added to a solution of sulfone
17 (2.46 g, 6.10 mmol) in absolute ethanol (50 mL).[32] The reaction
5.7 Hz, 1 H, 1-H), 4.25 (dd, J = 9.6, 5.6 Hz, 1 H, 1-H), 4.50 (s, 2 H, mixture was stirred for 24 h. The organic phase was separated, di-
PhCH2), 7.26–7.39 (m, 5 H, C6H5) ppm. 13C NMR (CDCl3): δ = luted with water (250 mL) and extracted with petroleum ether
13.4, 33.5, 36.7, 70.8, 71.7, 72.9, 127.4, 127.5, 128.2, 138.0 ppm.
C12H18O4S (258.3): calcd. C 55.79, H 7.02; found C 55.85, 7.00.
(5×30 mL). The combined organic phases were concentrated under
reduced pressure. Column chromatography of the residue on silica
gel (eluent: from petroleum ether to petroleum ether/ethyl acetate,
10:1) gave the title compound (1.13 g, 71%) as a colourless oil. IR
Tetrabutylammonium bromide (6.44 g, 20.0 mmol) was added to a
solution of (2R)-3-benzyloxy-2-methylpropyl methanesulfonate
(3.51 g, 13.6 mmol) in benzene (30 mL).[29] The reaction mixture
was stirred at 70 °C for 2 h (progress was monitored by thin-layer
chromatography on silica gel plates). After cooling to room tem-
perature, water (30 mL) was added. The aqueous phase was ex-
tracted with benzene (2×30 mL). The combined organic phases
were washed with water (20 mL), brine (20 mL), dried with MgSO4
and concentrated under reduced pressure to give bromide 15
(3.26 g, 99%) [α]D = –9.6 (c = 12.2, MeOH). The spectral data were
similar to those reported in the literature.[28e]
(CCl ): ν = 3040 cm–1. [α] = +3.9 (c = 12.8, EtOH). 1H NMR
˜
4
D
(400 MHz, CDCl3): δ = 0.89 (t, J = 6.5 Hz, 3 H, 10Ј-Me), 0.93 (d,
J = 6.7 Hz, 3 H, 2Ј-Me), 1.03–1.50 (m, 14 H, 3Ј-, 4Ј-, 5Ј-, 6Ј-, 7Ј-,
8Ј-, 9Ј-H), 1.75 (m, 1 H, 2Ј-H), 3.23 (dd, J = 9.1, 6.9 Hz, 1 H, 1Ј-
H), 3.33 (dd, J = 9.1, 6.1 Hz, 1 H, 1Ј-H), 4.49 (d, J = 12.1 Hz, 1
H, PhCH2), 4.52 (d, J = 12.1 Hz, 1 H, PhCH2), 7.24–7.41 (m, 5 H,
C6H5) ppm. 13C NMR (CDCl3): δ = 14.1, 17.1, 22.7, 26.9, 29.3,
29.6, 29.9, 31.9, 33.4, 33.6, 72.9, 76.0, 127.3, 127.5, 128.3,
138.8 ppm. C18H30O (262.4): calcd. C 82.38, H 11.52; found C
82.45, H 11.48.
(2R)-1-Benzyloxy-2-methyl-3-(phenylsulfonyl)propane (16): Tetrabu-
tylammonium benzenesulfinate[30] (7.66 g, 20.0 mmol) was added
to a solution of bromide 15 (2.92 g, 12.0 mmol) in benzene
(30 mL). The reaction mixture was stirred at 70 °C for 8 h and
treated with water (30 mL). The aqueous phase was extracted with
benzene (2×50 mL). The combined organic phases were washed
with water (30 mL), brine (30 mL), dried with Na2SO4 and concen-
trated under reduced pressure. Column chromatography on silica
gel (eluent: from petroleum ether to petroleum ether/ethyl acetate,
2:1) gave the title compound (3.26 g, 89%) as a colourless oil.
[α]D = +1.6 (c = 38.4, MeOH). The spectral data were similar to
those reported in the literature.[31]
(2S)-2-Methyldecan-1-ol (19): A solution of compound 18 (1.10 g,
4.20 mmol) in absolute EtOH (15 mL) was stirred under H2 in the
presence of 10% Pd/C (0.05 g) for 2 h. The mixture was filtered
and the filtrate concentrated under reduced pressure. Column
chromatography of the residue on silica gel (eluent: from petroleum
ether to petroleum ether/ethyl acetate, 5:1) gave the title compound
(0.68 g, 94%) as a colourless oil. The spectral data were similar to
those reported in the literature.[23]
(2S)-1-Bromo-2-methyldecane (20): A known method[29] was modi-
fied to suit the preparation of the title compound. A solution of
methanesulfonyl chloride (0.57 g, 5.0 mmol) in diethyl ether (5 mL)
was added dropwise at 0 °C to a stirred solution of alcohol 19
(0.65 g, 3.8 mmol) and triethylamine (0.77 g, 7.6 mmol) in diethyl
ether (15 mL). After stirring overnight, the reaction was quenched
with water (15 mL). The organic layer was separated and the aque-
ous layer was extracted with diethyl ether (3×25 mL). The com-
bined organic extracts were washed with brine (10 mL), dried with
MgSO4 and concentrated under reduced pressure to give a crude
mesylate, which was immediately dissolved in benzene (10 mL) con-
taining tetrabutylammonium bromide (1.61 g, 5.0 mmol). The solu-
tion was heated at 70 °C for 5 h. After cooling, water (5 mL) was
added. Extraction with petroleum ether (5×15 mL), drying over
MgSO4 and concentration under reduced pressure furnished a yel-
low oil, which after column chromatography on silica gel (eluent:
petroleum ether) gave the title bromide 20 (0.77 g, 87%). The spec-
tral data were similar to those reported in the literature.[23c]
(2R)-1-Benzyloxy-2-methyl-3-(phenylsulfonyl)decane (17): A solu-
tion of BuLi in hexane (18 mL, 1 , 18 mmol) was added dropwise
at –78 °C to a stirred solution of sulfone 16 (3.04 g, 10.0 mmol) in
a mixture of THF (26 mL) and HMPA (16 mL). The reaction mix-
ture was heated to –30 °C over the course of 2 h and then again
cooled to –78 °C. 1-Iodoheptane (4.52 g, 20.0 mmol) in hexane
(7 mL) was added dropwise to the reaction mixture. The resulting
solution was warmed to room temperature over 3 h and quenched
with water (20 mL). The aqueous phase was extracted with diethyl
ether (2×50 mL). The combined organic phases were washed with
brine (20 mL), dried with MgSO4 and concentrated under reduced
pressure. Column chromatography of the residue on silica gel (elu-
ent: from petroleum ether to petroleum ether/ethyl acetate, 2:1)
gave the title compound (2.78 g, 69%, syn/anti = 1:1) as a colourless
1
oil. IR (CCl ): ν = 3073, 3033 cm–1. H NMR (400 MHz, CDCl ):
˜
4
3
δ = 0.80 (t, J = 7.1 Hz, 1.5 H, 10-Me), 0.83 (t, J = 7.1 Hz, 1.5 H, (2S,3S)-3-Methyl-5-morpholino-5-oxopentan-2-ol (21): A solution
10-Me), 0.94 (d, J = 7.1 Hz, 1.5 H, 2-Me), 1.19 (d, J = 7.1 Hz, 1.5 of lactone 2 (cis/trans = 10:1, 1.63 g, 14.3 mmol) in morpholine
H, 2-Me), 1.02–1.36 (m, 10 H, 5-, 6-, 7-, 8-, 9-H), 1.46–1.62 (m, (15 mL) was heated at 100 °C for 24 h under argon. Morpholine
0.5 H, 4-H), 1.62–1.72 (m, 1 H, 4-H), 1.80–1.93 (m, 0.5 H, 4-H), was removed under reduced pressure. Column chromatography on
Eur. J. Org. Chem. 2006, 5069–5075
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5073

A. V. Bekish, K. N. Prokhorevich, O. G. Kulinkovich
FULL PAPER
silica gel (eluent: from ethyl acetate/cyclohexane, 1:1 to ethyl ace-
tate) gave crude 21 (2.45 g, 85%) as colourless crystals and lactone
2 (0.21 g, cis/trans = 3:1). Recrystallization from diethyl ether gave
pared from (2S)-2-methyl-1-bromodecane (20) (0.70 g, 3.0 mmol)
and lithium (0.05 g, 7.2 mmol) in diethyl ether (3 mL) at –20 °C
under argon. The solution obtained (with small unreacted lithium
amide 21 (syn/anti Ͼ 99:1, 1.73 g, 60%). M.p. 79–81 °C. [α]D = +3.5 shards) was cooled to –78 °C. A solution of amide 22 (0.33 g,
(c = 6.67, CH Cl ). IR (CHCl ): ν = 3645, 3390, 1655 cm–1. 1H 1.2 mmol) in THF (3 mL) was added dropwise over 5–10 min to the
˜
2
2
3
NMR (400 MHz, CDCl3): δ = 0.94 (d, J = 7.0 Hz, 3 H, 3-Me), stirred solution of (2R)-2-methyldecyllithium. The reaction mixture
1.13 (d, J = 6.2 Hz, 3 H, 1-H), 2.09–2.19 (m, 1 H, 3-H), 2.23 (dd, was stirred for 2 h at –78 °C and then quenched at the same tem-
J = 15.2, 6.2 Hz, 1 H, 4-H), 2.42 (br. s, 1 H, OH), 2.52 (dd, J =
perature first with MeOH (0.05 mL), and then with a saturated
15.2, 7.3 Hz, 1 H, 4-H), 3.47–3.55 (m, 2 H, NCH2), 3.59–3.69 (m, NH4Cl solution. The organic layer was separated and the aqueous
6 H, N-CH2, O-CH2), 3.84 (qd, J = 6.2, 3.1 Hz, 1 H, 2-H) ppm.
13C NMR (100 MHz, CDCl3): δ = 14.6, 19.2, 35.8, 36.2, 41.9, 46.2,
66.6, 66.8, 69.8, 171.7 ppm. C10H19NO3 (201.3): calcd. C 59.68, H
layer extracted with diethyl ether (3×5 mL). The combined organic
extracts were washed with brine, dried with Na2SO4 and concen-
trated under reduced pressure. Compound 23 (0.34 g, 83%) was
isolated by column chromatography on silica gel (eluent: petroleum
1
9.52; found C 59.62, H 9.47. H NMR (400 MHz, CDCl3) of the
isomeric (2S,3R)-3-methyl-5-morpholino-5-oxopentan-2-ol in the
region δ = 1.0–1.5 ppm: δ = 0.97 (d, J = 7.1 Hz, 3 H, 3-Me), 1.23
(d, J = 6.1 Hz, 3 H, 1-H) ppm (these signals were used to determine
the syn/anti ratio).
ether/ethyl acetate, 15:1) as a colourless oil. IR (CCl ): ν =
˜
4
1735 cm–1. 1H NMR (400 MHz, CDCl3): δ = 0.83–0.90 (m, 9 H,
3-Me, 7-Me, 15-H), 1.04 (d, J = 6.1 Hz, 1.5 H, 1-H), 1.13 (d, J =
6.4 Hz, 1.5 H, 1-H), 1.18–2.04 (m, 22 H, 3-, 7-, 8-, 9-, 10-, 11-, 12-
, 13-, 14-H, CH2CH2CH2 in tetrahydropyran), 2.11–2.29 (m, 2 H,
4-H or 6-H), 2.33–2.43 (m, 1 H, 4-H or 6-H), 2.51–2.59 (m, 0.5 H,
4-H or 6-H), 2.61–2.70 (m, 0.5 H, 4-H or 6-H), 3.42–3.51 (m, 1 H,
CHO or CH2O), 3.64–3.75 (m, 1 H, CHO or CH2O), 3.80–3.93 (m,
1 H, CHO or CH2O), 4.56–4.64 (m, 1 H, OCHO) ppm. C22H42O3
(354.6): calcd. C 74.52, H 11.94; found C 74.68, H 11.96.
Determination of the Enantiomeric Purity of 21: The ee value of 21
was determined by Mosher’s method[22a] from the integral inten-
sities of the doublets of the methyl groups at δ = 0.92 and 0.98 ppm
in the 1H NMR spectra of the (S)- and (R/S)-MTPA esters. In this
way the enantiomeric purity of compound 21 was determined to
be more than 98%.
(2S,3S,7S)-3,7-Dimethylpentadecan-2-ol (1): Powdered KOH (0.30 g,
5.4 mmol) was added to a solution of ketone 23 (0.33 g, 0.9 mmol)
and hydrazine hydrate (0.2 mL) in triethylene glycol (4.5 mL). The
reaction mixture was slowly (30 min) heated to 180 °C. Starting from
120 °C, a very weak flow of argon was periodically passed through
the solution in order to remove gaseous byproducts. The stirred reac-
tion mixture was heated at 180 °C for 1 h and then at 210 °C for
1.5 h. Then it was cooled to room temperature, diluted with water
(5 mL) and extracted with diethyl ether (3×7 mL). The combined
organic extracts were washed with a saturated NaHCO3 solution,
brine, dried with Na2SO4 and concentrated under reduced pressure.
The residue was dissolved in methanol (10 mL) and refluxed in the
presence of PPTS (0.02 g, 0.1 mmol) for 1 h. The solvent was re-
moved under reduced pressure. The target alcohol 1 (0.19 g, 80%
based on ketone 23) was isolated by column chromatography on
silica gel (eluent: petroleum ether/ethyl acetate, 15:1) as a colourless
oil. [α]D = –9.7 (c = 1.2, hexane). The spectral data were similar to
those reported in the literature.[3,4]
(1S,2S)-1,2-Dimethyl-4-morpholino-4-oxobutyl 3,3,3-Trifluoro-2-meth-
oxy-2-phenylpropanoate: H NMR (400 MHz, CDCl3): δ = 0.92 (d,
1
J = 6.8 Hz, 1.5 H, 2-Me), 0.98 (d, J = 6.8 Hz, 1.5 H, 2-Me), 1.27 (d,
J = 6.4 Hz, 1.5 H, 1-Me), 1.33 (d, J = 6.4 Hz, 1.5 H, 1-Me), 1.94–
2.37 (m, 3 H, 2- and 3-H), 3.15–3.32 (m, 2 H, N-CH2), 3.46 (s, 1.5
H, OMe), 3.55 (s, 1.5 H, OMe), 3.52–3.68 (m, 6 H, N-CH2 and O-
CH2), 5.10–5.19 (m, 1 H, 1-H), 7.29–7.65 (m, 5 H, aromatic H) ppm.
(1S,2S)-1,2-Dimethyl-4-morpholino-4-oxobutyl (2S)-3,3,3-Trifluoro-2-
methoxy-2-phenylpropanoate: 1H NMR (400 MHz, CDCl3): δ = 0.98
(d, J = 6.8 Hz, 3 H, 2-Me), 1.27 (d, J = 6.4 Hz, 3 H, 1-Me), 2.07
(dd, J = 16.4, 9.8 Hz, 1 H, 3-H), 2.27–2.37 (m, 2 H, 3-H and 2-H),
3.25–3.32 (m, 2 H, N-CH2), 3.46 (s, 3 H, OMe), 3.52–3.66 (m, 6 H,
N-CH2 and O-CH2), 5.12 (qd, J = 6.4, 2.9 Hz, 1 H, 1-H), 7.36–7.43
(m, 3 H, aromatic H), 7.47–7.55 (m, 2 H, aromatic H) ppm.
4-[(3S,4S)-3-Methyl-4-(tetrahydro-2H-pyran-2-yloxy)pentanoyl]-
morpholine (22): A solution of amide 21 (1.87 g, 9.29 mmol), 3,4-
dihydro-2H-pyran (1.56 g, 18.6 mmol) and PPTS (0.05 g,
0.2 mmol) in chloroform (20 mL) was refluxed for 3 h. The reaction
mixture was washed with a saturated NaHCO3 solution, the or-
ganic layer was separated and the aqueous layer was extracted with
chloroform (3×10 mL). The combined organic extracts were dried
with Na2SO4 and concentrated under reduced pressure. Compound
22 (2.63 g, 99%) was isolated by column chromatography on silica
(1S,2S,6S)-3,7-Dimethyl-2-pentadecyl Acetate (ac-1): CH3COCl
(0.15 mL, 2.1 mmol) was added in one portion at 0 °C to a stirred
solution of alcohol 1 (0.180 g, 0.70 mmol) and Et3N (0.59 mL,
4.2 mmol) in diethyl ether (3 mL). The reaction mixture was stirred
for 10 h at room temperature and then quenched with water (3 mL).
The organic layer was separated and the aqueous layer extracted
with diethyl ether (4×2 mL). The combined organic extracts were
dried with Na2SO4 and concentrated under reduced pressure. The
product (0.184 g, 88%) was isolated by column chromatography on
silica gel (eluent: petroleum ether/ethyl acetate, 25:1) as a colourless
oil. [α]D = –5.6 (c = 1.2, hexane). The spectral data were similar to
those reported in the literature.[3,4]
gel (eluent: petroleum ether/ethyl acetate, 2:1) as a colourless oil.
1
[α]D = –3.9 (c = 9.67, Et O). IR (CCl ): ν = 1665 cm–1. H NMR
˜
2
4
(400 MHz, CDCl3): δ = 0.94 (d, J = 6.9 Hz, 1.5 H, 3Ј-Me), 0.96
(d, J = 6.9 Hz, 1.5 H, 3Ј-Me), 1.07 (d, J = 6.5 Hz, 1.5 H, 5-H),
1.17 (d, J = 6.5 Hz, 1.5 H, 5-H), 1.42–1.86 (m, 6 H, CH2CH2CH2),
2.05 (dd, J = 10.5, 9.1 Hz, 0.5 H, 2Ј-H), 2.09 (dd, J = 10.5, 9.1 Hz,
0.5 H, 2Ј-H), 2.15–2.28 (m, 1 H, 3Ј-H), 2.53 (dd, J = 14.6, 4.2 Hz,
0.5 H, 2Ј-H), 2.67 (dd, J = 14.6, 4.5 Hz, 0.5 H, 2Ј-H), 3.42–3.97
(m, 11 H, 2-, 3-, 5-, 6-, 4Ј-H, CH2CH2CH2O), 4.59–4.64 (m, 1 H,
OCHO) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.9, 15.1, 15.5,
17.0, 20.0, 20.1, 25.28, 25.34, 31.1, 31.2, 34.35, 34.42, 35.46, 35.51,
41.72, 41.75, 45.9, 62.8, 63.1, 66.5, 66.6, 66.80, 66.82, 74.0, 76.6,
96.6, 98.8, 171.2, 171.5 ppm. C15H27NO4 (285.4): calcd. C 63.13,
H 9.54; found C 63.27, H 9.64.
Acknowledgments
We are grateful to the Forestry Ministry of the Republic of Belarus
for financial support.
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(2S,3S,7S)-3,7-Dimethyl-2-(tetrahydro-2H-pyran-2-yloxy)pentade-
can-5-one (23): A solution of (2R)-2-methyldecyllithium was pre-
5074
www.eurjoc.org
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2006, 5069–5075

Transformation of Esters into 2-Substituted Allyl Halides
FULL PAPER
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[11]
[12]
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1
Spectral data for lactone 10: IR (CCl ): ν = 1775, 1680 cm . H
˜
4
NMR (400 MHz, CDCl3): δ = 1.35 (d, J = 6.1 Hz, 3 H), 3.08–
3.22 (m, 2 H), 4.95–5.04 (m, 3 H) ppm. 13C NMR (CDCl3): δ =
20.5, 34.4, 78.0, 108.4, 143.5, 174.3 ppm.
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[14]
[15]
[16]
The spectral data for compound 11 are identical to those re-
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Received: June 5, 2006
Published Online: September 18, 2006
Eur. J. Org. Chem. 2006, 5069–5075
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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5075