Stereoselective allylation of chiral monoperoxyacetals

Article abstract of DOI:10.1016/j.tet.2005.02.071

Neighboring iodo-, alkoxy-, acetoxy- and silyl groups impart useful levels of diastereoselection in the Lewis acid-mediated allylation of monoperoxyacetals. Although monoperoxyacetals are found to be considerably less reactive than corresponding nonperoxi

Full text of DOI:10.1016/j.tet.2005.02.071

Tetrahedron 61 (2005) 4657–4670
Stereoselective allylation of chiral monoperoxyacetals
*
Aqeel Ahmed and Patrick H. Dussault
Department of Chemistry, University of Nebraska-Lincoln, Lincoln, NE 68588-0304, USA
Received 8 October 2004; revised 21 February 2005; accepted 24 February 2005
Available online 6 April 2005
Abstract—Neighboring iodo-, alkoxy-, acetoxy- and silyl groups impart useful levels of diastereoselection in the Lewis acid-mediated
allylation of monoperoxyacetals. Although monoperoxyacetals are found to be considerably less reactive than corresponding nonperoxidic
acetals, similar stereochemical trends are observed in the two series.
q 2005 Elsevier Ltd. All rights reserved.
1. Introduction
from a resident stereocenter in the peroxyacetal backbone.
This approach, while unexplored in peroxide chemistry, has
precedent in the chemistry of simple acetals. For example,
Cram–Felkin–Anh (CFA) stereoinduction has been demon-
strated in reactions of acetals.5 However, effective CFA
directing groups are rarely practical in terms of the
conditions required for synthetic modification or removal.
We were intrigued by reports of diastereoselective dis-
placements of nonperoxidic acetals based upon induction
from neighboring heteroatoms.6,7 We now report on the
Lewis acid-mediated displacement of halo-, alkoxy, acyl-
oxy, and silyl-substituted monoperoxyacetals. (Fig. 2).
Although the number of reported peroxide natural products
continues to increase, methodology for peroxide synthesis
remains limited.1,2 For example, there exist only a handful
of approaches to homoallyl peroxides and 3-peroxyalk-
anoates, common subunits in peroxide natural products;
some typical examples are illustrated in Figure 1. We have
reported new methodology for introduction of these
substructures based upon Lewis acid-mediated reactions
of monoperoxyacetals with electron-rich alkenes.3,4 We
sought to extend this methodology to asymmetric synthesis
and we now report the stereoselective allylation of
monoperoxyacetals based upon stereoinduction from neigh-
boring chiral centers.
Figure 2. Overview.
2. Results and discussion
Our studies focused on induction from 2-, 3-, and 4-substi-
tuted monoperoxyacetals (Fig. 2).
Figure 1. Naturally occurring homoallyl peroxides and 3-peroxy-
alkanoates.
2.1. Preparation of substrates
The Lewis acid-mediated reactions of peroxyacetals appear
to involve ionization to intermediate peroxycarbenium
ions,3 a mechanism which limits the stereochemical
influence of the departing alkoxide, the Lewis acid, or the
acetal center. We therefore chose to investigate induction
Preparation of 2-halo- and 2-mercurioperoxyacetals is
illustrated in Table 1. Enol ethers 1 and 2 were prepared
as isomeric mixtures and reacted with t-butyl hydroperoxide
in the presence of NIS, NBS, or mercuric acetate to furnish
2-halo or 2-mercurioperoxyacetals as mixtures of diastereo-
mers.8 The diastereomeric 2-mercurioperoxyacetals were
easily separated. The isomeric 2-haloperoxyacetals were
inseparable but mixtures enriched in one diastereomer
Keywords: Peroxide; Monoperoxyacetal; Allylation; Lewis acid; Stereo-
induction; Neighbouring group.
*
Corresponding author. Tel.: C1 402 4723634; fax: C1 402 4722044;
e-mail: pdussaultl@unl.edu
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.02.071

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A. Ahmed, P. H. Dussault / Tetrahedron 61 (2005) 4657–4670
Table 1. Synthesis of 2-halo/mercurioperoxyacetals
triphenylsilane (7) led only to decomposition. Attempts to
prepare 2-mercapto monoperoxyacetals by a similar
approach involving ozonolysis of allyl sulfides (not
shown) were uniformly unsuccessful.
A series of 3-oxygenated peroxyacetals 12a–i were prepared
through ozonolysis of unsaturated ethers and esters,
followed by silylation of the derived hydroperoxyacetals
(Table 3). In each case, the new peroxyacetals were formed
as 1:1 mixtures of epimers. Two 4-substituted peroxyacetals
were prepared by a similar procedure (Table 4).
Substrate
Oxidant
Product
X
Yield (%)
1
1
1
2
NIS
NBS
Hg(OAc)2
NIS
3a
3b
3c
4a
I
Br
HgCl
I
60
45
80
47
Table 4. Synthesis of 4-substituted monoperoxyacetals
were available based upon peroxyhalogenation of samples
of enol ether enriched in the E-isomer. The halo- and chloro-
mercurioperoxyacetals were quite stable, except for iodo-
acetal 3a, which decomposed upon prolonged storage.
Substrate
X
Product
Yield
13a
13b
OMe
I
14a
14b
40
34
The preparation of 2-silyl peroxyacetals, an unknown class
of compounds, was initially modeled for an achiral substrate
(Table 2). Ozonolysis of allyltriphenylsilane in 2-methoxy-
ethanol cleanly furnished a 2-triphenylsilyl hydroperoxy-
acetal, which underwent O-silylation to furnish
peroxyacetal 5.9 Ozonolysis of chiral trialkylsilane 6
furnished an 85:15 mixture of diastereomeric 2-silyl
hydroperoxyacetals, a result demonstrating significant
influence of the trialkylsilyl group on the intermediate
carbonyl oxide. Curiously, ozonolysis of the analogous
2.2. Lewis acid-mediated reactions
Allylations were initially investigated for 3-substituted
peroxyacetals (Table 5). Optimal conditions were found to
involve addition of stoichiometric SnCl4 to a 0 8C solution
of the peroxyacetal and allylsilane.3 Reactions were
generally complete within one to 2 h. The products were
isolated and purified by standard methods, with diastereo-
selectivity determined by NMR integration; control experi-
ments demonstrated no difference in diastereomer ratios
before or after purification. Ether 12b and the pivaloate ester
12f reacted with moderate syn selectivity (vide infra);
diastereoselection was reduced in the case of the acetate
(12d) or benzoate (12e) and nonexistent for the silyloxy
peroxyacetal (12a). A benzylic monoperoxyacetal (12h)
and the sole monoperoxyketal (12i) underwent predominant
decomposition under the reaction conditions (not shown).
Table 2. Synthesis of 2-silyl monoperoxyacetals
Substrate
R
X
Product
AllySiPh3
6
7
H
Hexyl
Hexyl
SiPh3
SiMe2tBu
SiPh3
5 (45%)
8 (54%)
—
Table 5. Allylation of 3-oxygenated peroxyacetals
Table 3. Synthesis of 3-oxygenated peroxyacetals
S. mat.
R
Product
Yield (%)
syn/anti
12a
12b
12c
12d
12e
12f
SiMe2t-Bu
15a
15b
15c
15d
15e
15f
65
60
50
60
55
55
50:50
75:25
60:40
60:40
62:38
73:27
Me
Bn
Ac
Bz
Piv
R
R1
R2
X
11a–i
(%)
12a–i
(%)
Monoperoxyacetal 12g, a substrate intended to explore
1,5-stereoinduction via ethereal oxygen, instead revealed
the tremendous difference in reactivity between peroxidic
and nonperoxidic acetals; both major products resulted from
initial allylation of the MOM group (Eq. 1). To our
knowledge, this is the first direct comparison of the
reactivity of an acetal and a monoperoxyacetal under
ionizing conditions.
10a
10b
10c
10d
10e
10f
10g
10h
10i
Heptyl
Heptyl
Heptyl
Heptyl
Heptyl
Heptyl
Heptyl
Ph
TBS
Me
Bn
Ac
Bz
Piv
MOM
Ac
H
H
H
H
H
H
H
H
Me
OMe
H
H
H
H
H
H
H
H
73
45
45
60
40
50
55
50
62
85
87
88
77
75
60
82
55
75
Hexyl
Ac

A. Ahmed, P. H. Dussault / Tetrahedron 61 (2005) 4657–4670
4659
1,2-Stereoinduction. The observed diastereoselectivity for
allylation of 2-iodoperoxyacetal 3a varied somewhat
depending upon the composition of the starting material
but consistently afforded one major diastereomer (Table 6).
The major product was assigned as anti based upon spectral
correlations with reports for 2-iodoethers5 and 2-iodo-
peroxides.11 Intriguingly, iodoacetal 3a underwent allyla-
tion at K78 8C, whereas most other peroxyacetals,
including the closely related 4a, undergo reaction only at
temperatures near 0 8C. In addition, significant decompo-
sition of 3a was observed under the reaction conditions.
The 2-bromoperoxyacetal 3b was unreactive while the
2-chloromercurioperoxyacetal underwent rapid decompo-
sitioninthepresenceofeitherSnCl4 orTMSOTf(notshown).
(1)
Peroxyacetal 18 was investigated as a substrate in which
interaction of the ester carbonyl with the developing
peroxycarbenium ion would provide a transient cyclic
framework for stereoinduction from the 3-trimethylsilyl
group. Diastereoselection in formation of the homoallyl
peroxide was similar to that obtained for the 3-alkoxy and
3-acyloxy substrates shown above (Eq. 2).
Table 6. Allylation of 2-iodoperoxyacetals
(2)
We also investigated 1,3-stereoinduction through a tempo-
rary scaffold (Scheme 1). Ozonolysis of a homoallylic
alcohol followed by bissilylation of the derived hydro-
peroxyalcohol achieved the first synthesis of a 3-sila-1,2,4-
trioxepane (20). Unfortunately, this substrate was nearly
unreactive, furnishing !5% yield of allylated silatrioxe-
pane under typical reaction conditions; attempted reaction at
higher temperatures resulted in decomposition.
S. mat.
dr
T (8C)
Product
(yield)
syn/anti
3a
3a
4a
4a
40:60
75:25
76:24
71:29a
K78
K78
0
26 (30%)
26 (28%)
27 (23%)
27 (20%)
1:1.4
1:9
1:3
0
1:5
a Conducted in 25% CH3NO2/CH2Cl2.
Investigation of 1,2 stereoinduction from a silyl group was
thwarted by the decomposition of silyl peroxyacetal 8 under
the reaction conditions (Scheme 3). This failure was curious,
given the successful allylation of the achiral model (5).
Scheme 1. Allylation of alkoxysilatrioxepane. (a) O3, 2-methoxyethanol;
(b) t-Bu2Si(OTf)2, DMF, imidazole; (c) allyltrimethylsilane, SnCl4, 0 8C.
Stereochemical correlation. The major diastereomers for
the 3-alkoxy- and 3-acyloxyhomoallyl peroxides 15c and
15d were assigned as syn based upon the 13C chemical shifts
of the derived 1,3-dioxanes 23 and 25 (Scheme 2).10
Scheme 3. Allylation of 2-silyl monoperoxyacetals.
1,4-Stereoinduction. Allylation of the 4-methoxyl peroxy-
acetal 14a proceeded in good yield and with moderate
stereoselection; the 4-iodoperoxyacetal (14b) underwent
allylation in lower yield and with reduced diastereoselection
(Table 7).
Table 7. Allylation of 4-substituted monoperoxyacetals
Substrate
X
Product
Yield (%)
dr
14a
14b
OMe
I
29a
29b
78
30
71:29
60:40
Scheme 2. Stereochemical correlation. (a) LiAlH4; (b) 2,2-dimethoxypro-
pane, CSA; (c) THF/HOAc/H2O; (d) PPh3; (e) Pd/H2.

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A. Ahmed, P. H. Dussault / Tetrahedron 61 (2005) 4657–4670
2.3. Discussion
3. Conclusion
Our results demonstrate the influence of neighboring
heteroatoms on the reactivity of peroxyacetals and the
stereoselectivity of peroxyacetal displacement. The
degree of influence is dependent upon the nature and
location of the group. Peroxyacetals bearing 3-alkoxy
and 3-acyloxy substituents are as reactive as unsub-
stituted monoperoxyacetals,2 suggesting only limited
influence of b-oxygenation on the barriers to substrate
ionization. However, the syn selectivity observed for
reactions of 3-methoxy and 3-pivaloyloxy peroxyacetals,
and the complete lack of selectivity for the 3-tri-
alkylsiloxy substrate, indicates the importance of
interactions with the intermediate peroxycarbenium
ion; in the case of the 3-acyloxy groups, the
diastereoselection varies with the bulk of the side
chain. The outcome with the trialkylsiloxy group is
similar to results observed with 3-silyloxyaldehydes
(Eq. 3).12 Our results provide a mechanistic under-
pinning for results reported for reactions of 3-alkoxy
acetals.5 Moderate stereochemical induction is also
observed for the 4-methoxyperoxyacetal, although the
selectivity is lower than that reported for reactions of
4-alkoxyacetals.7
Easily installed and synthetically tractable neighboring
groups are shown to impart useful levels of stereoinduction
to the allylation of monoperoxyacetals. The results, while
paralleling previous findings for reactions of nonperoxidic
acetals, are influenced by the unique reactivity patterns of
the peroxyacetals. Application of these results to the
synthesis of peroxide natural products is under
investigation.
4. Experimental
4.1. General
Standard experimental procedures have been described
elsewhere.13 All new compounds were determined to be
O95% pure based upon 1H or 13C NMR. Unless otherwise
noted NMR spectra were recorded at 500 (1H) or 125 (13C)
MHz in CDCl3. FT-IR spectra were recorded as CH2Cl2
or CDCl3 solutions; selected absorbances are reported in
cmK1. Most hydroperoxides and peroxides failed to
generate identifiable molecular or fragmentation ions
(HRFAB or HREI).
4.1.1. (E)- and (Z)-1-Methoxy-1-nonene (1). The title
compounds were prepared as a mixture from octanal.14
4.1.2. (E)- and (Z)-1-(2-Methoxyethoxy)-oct-1-ene (2).
The title compounds were prepared using a variation of a
reported procedure.15 Into a solution of 1-octanal (2.0 g,
16 mmol) in 2-methoxyethanol (50 mL) was added
p-TsOH$H2O (cat., 100 mg). The reaction was stirred for
15 min and then quenched with sat. NH4Cl solution.
(100 mL) The Et2O extracts (2!50 mL) were dried over
Na2SO4 and concentrated. Flash chromatography (20% EA/
Hex) furnished 1,1-bis-(2-ethoxymethoxy)-octane (3.7 g,
90%). RfZ0.48 (20% EA/hex); 1H d 4.53 (t, 1H, JZ
6.0 Hz), 3.65 (m, 2H), 3.56 (m, 2H), 3.47 (t, 4H, JZ4.7 Hz),
3.30 (s, 6H), 1.59–1.55 (2H), 1.30–1.20 (10H), 0.80 (t, 3H,
JZ6.6 Hz); 13C d 103.2, 71.9, 63.9, 58.7, 32.9, 31.6, 29.2,
29.0, 24.5, 22.4, 13.8; IR 1129; HRFAB calcd for
C14H30O4Li (MCLi)C: 269.2304; found: 269.2317,
4.9 ppm.
(3)
The enhanced reactivity of 2-iodo and 2-triphenylsilyl
peroxyacetals suggests a significant influence on sub-
strate ionization. Allylation of the 2-iodoperoxyacetals
proceeds with higher diastereoselectivity than for any of
the other substrates studied. This, combined with the
consistent preference for formation of the anti dia-
stereomer, suggests a strong interaction with a peroxy-
carbenium ion or similar species. At the same time, the
variation in product diastereoselection depending upon
the composition of the starting material suggests the
possibility of reaction through both intimate versus
separated ion pairs (Eq. 4). While the chiral 2-tri-
alkylsilyl peroxyacetals underwent decomposition under
reaction conditions, it is interesting to note that the
2-trialkylsilyl group exerted a very strong influence on
the stereochemistry of trapping of a neighboring
carbonyl oxide.
A solution of the bis-methoxyethoxy acetal (2.9 g,
11 mmol) and diisopropylethylamine (50 mL) was heated
to 115–120 8C in an oil bath whereupon trimethylsilyl
trifluoromethanesulfonate (2.7 g, 12 mmol, 2.2 mL) was
rapidly added. After 2 min, the oil bath was removed and the
reaction was quenched with 10% NaOH (50 mL) and
hexanes (100 mL). The organic layer was washed with 10%
NaOH (2!25 mL) and water (50 mL), dried over Na2SO4
and concentrated. The DIPEA was removed under vacuum
and the crude product was purified by flash chromatography
to furnish 1-2-(methoxyethoxy)-oct-1-ene (2) as a colorless
liquid consisting of a 1:4.2 mixture of E and Z isomers
1
(1.4 g, 70%): RfZ0.44 (2% EA/hex); H d 6.25 (d, 0.2H,
(4)
JZ12.6 Hz), 5.94 (d, 0.8H, JZ6.3 Hz), 4.78 (dt, 0.2H, JZ
12.6, 7.2 Hz), 4.34 (dd, 0.8H, JZ6.9, 7.2 Hz), 3.84 (t, 1.6H,
JZ4.7 Hz), 3.78 (t, 0.4H, JZ4.7 Hz), 3.59 (t, 0.4H, JZ
4.7 Hz), 3.56 (t, 1.6H, JZ4.7 Hz), 3.39 (s, 0.8H), 3.387 (s,

A. Ahmed, P. H. Dussault / Tetrahedron 61 (2005) 4657–4670
4661
2.2H), 2.09–2.05 (1.6H), 1.91–1.87 (0.4H), 1.31–1.27 (8H),
0.87 (t, 3H, JZ6.9 Hz); 13C d 146.0, 144.7, 107.8, 104.7,
71.7, 71.24, 71.21, 68.2, 59.09/59.04, 31.74/31.70, 30.6,
29.7, 28.9, 28.6, 27.6, 23.9, 22.6, 14.0; IR 1660, 1101;
HRFAB calcd for C11H22O2Li (MCLi)C: 193.1780; found:
193.1774 (3.1 ppm).
hexanes (50 mL). The solution was washed with satd
NaCl (3!100 mL) and dried over Na2SO4 The precipitate
obtained upon concentration was suspended in hexanes
(50 mL) and filtered through a plug of cotton. Removal of
solvent in vacuo followed by purification through flash
silica (5% EA/hex) furnished colorless oil (1.3 g, 80%) as a
mixture of diastereomers, which were easily separated by
HPLC (4.6!25 mm Si, 5% EA/hex, 10 mL/min, 13.6 min,
17.0 min). First eluting diastereomer: RfZ0.33 (5% EA/
hex); 1H d 4.96 (d, 1H, JZ2.5 Hz), 3.55 (s, 3H), 2.68–2.64
(m, 1H), 1.80–1.58 (2H), 1.48–1.28 (8H), 1.26–1.25 (11H),
0.87 (t, 3H, JZ6.6 Hz). 13C 109.2, 80.9, 57.3, 32.5, 31.7,
31.0, 29.3, 29.0, 26.6, 24.7, 22.5, 14.0. Second eluting
4.1.3. (syn)- and (anti)-1-tert-Butylperoxy-2-iodo-1-
methoxynonane (3a). A solution of 70% aqueous tert-
BuOOH (10 mL) was extracted with CH2Cl2 (10 mL). The
organic layer was successively dried over Na2SO4 and
MgSO4 and 4 mL of the resulting solution was added into
solution of enol ether 1 (1.0 equiv, 3.6 mmol, 570 mg) in
CH2Cl2 (10 mL). The mixture was cooled to K78 8C and
N-iodosuccinimide (1.5 equiv, 5.5 mmol, 1.23 g) was
added. The reaction flask was briefly removed from cooling
bath whenever the mixture solidified. After 15 min the
reaction was quenched with DI water and extracted with
CH2Cl2 (2!25 mL). The combined organic layers were
dried over Na2SO4 and concentrated. The residue was
redissolved into 2% EA/hex (50 mL) and stirred over a
pinch of charcoal until the reddish violet color was lost
(ca. 15 min). The solution was filtered through a plug of
cotton and concentrated under reduced pressure. Flash
chromatography furnished 0.82 g (60%) of 3a as a mixture
of diastereomers which could not be completely separated.
1
diastereomer: RfZ0.33 (5% EA/hex); H 4.98 (d, 1H, JZ
3.8 Hz), 3.49 (s, 3H), 2.6–2.56 (m, 1H), 1.83–1.57 (2H),
1.47–1.29 (6H), 1.27–1.23 (13H), 0.86 (t, 3H, JZ6.9 Hz);
13C d 108.8, 80.9, 56.79, 56.77, 54.6, 32.3, 31.7, 30.5, 29.3,
29.0, 26.6, 22.5, 13.93, 13.91; IR (cmK1): 2924–2854, 1464,
1366, 1181, 1105; HRMS (FAB/EI) observed only high
molecular weight ion aggregates.
4.1.6. syn- and anti-1-tert-Butylperoxy-2-iodo-1-(2-meth-
oxyethoxy)-octane (4a). Into a K25 8C solution of enol
ether 2 (845 mg, 4.5 mmol) in CH2Cl2 (10 mL) was added
tert-BuOOH (5 mL of a 5.0–6.0 M solution in nonane),
followed by N-iodosuccinimide (1.5 g, 6.8 mmol,
1.5 equiv). The reaction was stirred for 5 min and then
quenched with DI water. The Et2O extracts (2!50 mL)
were dried over Na2SO4 and concentrated. Workup and
purification as for iodoacetal 3a furnished 0.85 g (47%) of
4a as a 4:1 mixture of diastereomers which could not be
1
RfZ0.6 (2% EA/hex); H d 4.78 (d, 0.7H, 4.4), 4.57 (d,
0.3H, 5.0), 4.09–4.04 (m, 1H), 3.575 (s, 1.8H), 3.57 (s,
1.2H), 1.78–1.73 (2H), 1.55–1.47 (2H), 1.32–1.19 (17H,
including obscured singlets from tert-Bu), 0.85 (t, 3H, JZ
6.9 Hz); 13C d 108.3/107.8, 80.9/80.7, 58.0/57.9, 34.8, 33.9,
33.2, 32.6, 31.7, 29.4, 29.37, 29.3, 29.0, 28.7, 28.6, 26.5,
22.5, 13.96; IR 2977–2851, 1358, 1249, 1199, 1110;
HRFAB calcd for C13H26IO2 (MKOMe)C: 341.0978;
found: 341.1177 (58.3 ppm).
1
cleanly separated. RfZ0.38 (2% EA/hex); H d 4.92 (d,
0.8H, JZ5.0 Hz), 4.77 (d, 0.2H, JZ5.0 Hz), 4.10–4.03
(2H), 3.86–3.81 (1H), 3.61–3.54 (2H), 3.38 (s, 3H), 1.84–
1.74 (2H), 1.58–1.32 (8H), 1.27 (s, 6.3H), 1.268 (s, 2.7H),
0.87 (t, 3H, JZ6.9 Hz); 13C d 107.4, 107.0, 81.0, 71.95/
71.91, 69.79/69.76, 59.0, 34.3, 32.8, 31.60/31.57, 29.3,
28.41, 28.36, 26.6, 22.5, 14.0; IR 1242, 1195, 1125; HRFAB
calcd for C15H31IO4Li (MCLi)C: 409.1427; found:
409.1432 (1.1 ppm).
4.1.4. syn- and anti-2-Bromo-1-tert-butylperoxy-1-meth-
oxy-nonane (3b). Into a K20 8C solution of enol ether
(522 mg, 3.3 mmol) and tert-BuOOH in CH2Cl2 (5 mL) was
added NBS (2.0 equiv, 1.2 g). After 15 min, the reaction
mixture was quenched with DI water, and extracted with
recycled EA/Hex (3!30 mL). The organic layers were
dried over Na2SO4 and concentrated in vacuo. Flash
chromatography (hexanes or n-pentane) furnished 490 mg
(45%) of a mixture of diastereomeric bromo peroxy acetals:
4.1.7. 1-(2-Methoxyethoxy)-2-triphenylsilyl ethyl tert-
butyl dimethylsilyl peroxide (5). YieldZ0.65 g, 50%.
1-(2-Methoxyethoxy)-2-triphenylsilyl ethyl hydroperoxide
was prepared by ozonolysis of allyltriphenylsilane in
2-methoxyethanol using the procedure described for homo-
allyl ethers and esters (vide infra). RfZ0.52 (50% EA/hex);
1H (400 MHz) d 10.58 (s, 1H), 7.72–7.69 (6H), 7.49–7.40
(9H), 5.19 (dd, 1H, JZ4.5, 8.3 Hz), 3.62–3.48 (3H), 3.47–
3.41 (1H), 3.4 (s, 3H), 2.24 (dd, 1H, JZ8.3, 14.9 Hz), 2.05
(dd, 1H, JZ4.5, 15.2 Hz). 13C (100 MHz) d 135.5, 134.1,
129.2, 127.5, 105.5, 72.2, 65.1, 58.5, 17.5; IR 3306 (broad),
1481, 1350, 1196, 1128; HRMS: no identifiable ions were
observed.
1
RfZ0.7 (n-pentane); H d 4.88 (d, 0.5H, JZ4.7 Hz), 4.79
(d, 0.5H, JZ5.4 Hz), 4.04–3.98 (m, 1H), 3.59 (s, 1.7H),
3.58 (s, 1.3H), 1.99–1.89 (2H), 1.8–1.71 (2H), 1.41–1.21
(17H), 0.87 (t, 3H, JZ6.9 Hz); 13C d 108.0/107.7, 81.0,
58.02/57.94, 53.6/52.8, 33.2, 32.7, 31.8, 31.7, 29.0, 28.9,
28.8, 27.25, 27.24, 26.6, 26.5, 22.5, 14.0; IR 2924–2858,
1238, 1192, 1102; HRMS: no identifiable ions were
observed.
4.1.5. syn- and anti-1-tert-Butylperoxy-2-chloromer-
curio-1-methoxynonane (3c). To a solution of Hg(OAc)2
(1.1 equiv, 3.70 mmol, 1.18 g) and tert-BuOOH in CH2Cl2
(5 mL) in an ice bath was added, dropwise, enol ether 1
(1.0 equiv, 3.4 mmol, 525 mg) as a solution in CH2Cl2
(10 mL). After the addition was complete, the reaction was
allowed to warm to room temperature and stirred until the
salt had dissolved (5 min). Solvent was removed under
reduced pressure and the residue was diluted with
Silylation of the hydroperoxyacetal under standard con-
ditions (vide infra) furnished the silyl peroxyacetal 5:
YieldZ429 mg, 90%. RfZ0.35 (5% EA/hex); 1H
(400 MHz) d 7.66–7.64 (6H), 7.48–7.40 (9H), 5.11 (dd,
1H, JZ4.3, 8.1 Hz), 4.06 (m, 1H), 3.43 (m, 1H), 3.32 (m,
1H), 3.32 (t, 2H, JZ5.05 Hz) 3.296 (s, 3H), 2.13 (dd, 1H,
JZ8.1, 14.9 Hz), 1.92 (dd, 1H, JZ4.3, 14.9 Hz), 0.98
(s, 9H), 0.19 (s, 3H), 0.13 (s, 3H). 13C (100 MHz) d 135.7,

4662
A. Ahmed, P. H. Dussault / Tetrahedron 61 (2005) 4657–4670
134.6, 129.4, 127.7, 106.9, 71.6, 69.4, 58.6, 26.1, 18.0,
K5.7, K5.8; IR 1473, 1326, 1188, 1124. HRFAB calcd for
C29H40O4Si2Li (MCLi)C: 515.2625; found: 515.2620
(1.0 ppm).
4.2.2. 4-Methoxyundec-1-ene (10b). To a 1.0 M solution of
undec-1-ene-4-ol (650 mg, 3.8 mmol) in DMF was added
NaH (305 mg, 60% suspension in mineral oil, 7.6 mmol),
MeI (0.3 mL, 5 mmol), 6.8 mmol), Py (0.6 mL, 6.8 mmol)
at 0 8C and the reaction mixture was stirred overnight
(convenience). The reaction mixture was quenched with
satd NH4Cl and extracted with recycled 20% EA/hexanes
(3!25 mL), the organics were dried over Na2SO4 and the
solvent was removed under reduced pressure. Flash
chromatography (5% EA/hexanes) of the crude product
furnished 493 mg (70%) of the methyl ether. RfZ0.42 (5%
4.1.8. tert-Butyldimethyl(1-nonen-3-yl)silane (6). The
title compound was prepared by C-silylation of octanal
tert-butylimine followed by Wittig methylenation of the
derived aldehyde.16
4.1.9. 1-Nonen-3-yl triphenylsilane (7). The title com-
pound was prepared by a similar procedure as for 6; the
yield for methylenation was less than 5% (812 mg). RfZ
1
EA/hex); H d 5.89 (ddt, 1H, JZ17.6, 10.1, 6.9 Hz), 5.07
(dd, 1H, JZ17.3, 1.9 Hz), 5.04 (dd, 1H, JZ10.1, 1.8 Hz),
3.33 (s, 3H), 3.19–3.18 (m, 1H), 2.28–2.24 (m, 2H), 1.47–
1.35 (12H), 0.87 (t, 3H, JZ6.9 Hz); 13C d 135.1, 116.6,
80.6, 56.5, 37.8, 33.4, 31.8, 29.7, 29.3, 25.3, 22.6, 14.0; IR
1643, 1100; HREI: calcd for C12H23O (MKH)C: 183.1747,
found: 183.1744 (2.8 ppm).
1
0.72 (2% EA/hex); H (400 MHz) d 7.58–7.55 (6H), 7.43–
7.33 (9H), 5.71 (ddd, 1H, JZ16.9, 10.1, 7.0 Hz), 4.96
(broad d, 1H, JZ10.4, 1.5 Hz), 4.90 (broad d, 1H, JZ
17.2 Hz), 2.48 (td, 1H, JZ10.6, 7.5 Hz), 1.75–1.70 (1H),
1.50–1.42 (2H), 1.26–1.14 (7H), 0.85 (t, 3H, JZ7.3 Hz).
13C (100 MHz) d 138.9, 136.2, 134.2, 129.3, 127.7, 114.6,
32.1, 31.8, 29.0, 28.9, 22.6, 14.1; IR 1623, 1489, 1469,
1429; HRFAB calcd for C27H32SiLi (MCLi)C: 391.2433,
found: 391.2442 (2.3 ppm).
4.2.3. 4-Benzyloxy-undec-1-ene (10c). To a 1.0 M solution
of undec-1-ene-4-ol (2.0 g, 12.0 mmol) in DMF was added
neat NaH (0.58 g 24 mmol), BnBr (2.2 mL, 18 mmol), and a
catalytic amount of Bu4NI at 0 8C and the reaction mixture
was stirred overnight (convenience). The reaction mixture
was quenched with satd NH4Cl and extracted with recycled
20% EA/hexanes (3!50 mL), the organics were dried over
Na2SO4 and the solvent was removed under reduced
pressure. Flash chromatography (5% EA/hexanes) of the
crude product furnished 2.12 g (70%) of the methyl ether
(w5 g scale, 63%). RfZ0.69 (5% EA/hex); 1H d 7.43–7.40
(5H), 5.93 (ddt, 1H, JZ17.3, 10.1, 7.2 Hz), 5.23 (dd, 1H,
JZ17.3, 2.2 Hz), 5.17 (dd, 1H, JZ10.1, 2.2 Hz), 4.60 (d,
1H, JZ2.7 Hz), 4.58 (d, 1H, JZ2.7 Hz), 3.50 (m, 1H), 2.39
(dd, 2H, JZ2.9, 1.4 Hz), 1.65–1.30 (12H), 0.96 (t, 3H, JZ
6.9 Hz); 13C d 139.1, 135.1, 128.2, 127.6, 127.3, 116.6,
70.9, 38.3, 33.8, 31.8, 29.7, 29.2, 25.3, 22.6, 14.0; IR 1639,
1492, 1454, 1205, 1096; HREI: calcd for C18H28O (M)C:
260.2140, found: 260.2134 (2.3 ppm).
4.1.10. 2-(tert-Butyldimethylsilyl)-1-(2-methoxyethoxy)-
oct-1-yl tert-butyldimethylsilyl peroxide (8). Ozonolysis
of allylsilane 6 as above gave 2-(tert-butyldimethylsilyl)-1-
(2-methoxyethoxy)-octyl hydroperoxide (1.7 g, 60% yield).
RfZ0.48 (10% EA/hex); 1H d 10.38 (s, 1H), 5.04 (d, 0.2H,
JZ5.36 Hz), 4.88 (d, 0.8H, JZ6.6 Hz), 3.94–3.82 (m, 2H),
3.67–3.63 (m, 1H), 3.55–3.53 (m, 1H), 3.44 (s, 3H), 1.44–
1.26 (13H), 0.89 (s, 9H), 0.07 (s, 0.5H), 0.04 (s, 0.8H), 0.017
(s, 2H), 0.01 (s, 2.7H). 13C d 111.5/111.3, 73.4/73.3, 68.2,
67.7, 59.1, 59.0, 31.8, 31.7, 30.6, 30.5, 30.1, 29.7, 29.0,
28.4, 27.8, 27.5, 27.3, 27.25, 27.17, 26.7, 22.7/22.6, 17.7,
17.5, 14.1, K5.04/-5.15, K5.4/-5.8;IR3324(b), 1136 cmK1
.
HRMS: no identifiable ions were observed.
Silylation of this hydroperoxide under standard conditions
furnished silyl peroxyacetal 8 in 1.1 g, 90% yield: RfZ0.63
(10% EA/hex); 1H d 5.04 (d, 0.1H, JZ2.5 Hz), 5.0 (d, 0.9H,
JZ3.5 Hz), 4.17 (m, 0.1H), 4.13 (m, 0.9H), 3.77 (m, 1H),
3.52 (m, 2H), 3.359 (s, 2.5H), 3.554 (s, 0.5H), 1.53–1.253
(13H), 1.11 (m, 1H), 0.93 (s, 9H), 0.89–0.87 (3H), 0.88
(s, 9H), 0.17 (s, 2.8H), 0.16 (s, 3.2H), 0.05 (s, 2.9H), 0.03
(s, 3H); 13C d 111.7, 111.5, 72.4, 72.3, 70.6, 58.8, 31.9, 31.8,
30.3, 29.6, 28.9, 27.7, 27.2, 27.1, 26.2, 25.6, 22.7, 18.0,
17.4, 14.1, 14.0, K4.56, K5.47, K5.5, K5.9; IR 1132,
1104. HRFAB calcd for C23H52O4Si2Na (MCNa)C:
471.3304, found: 471.3313 (2.3 ppm).
4.2.4. Acetic acid, 1-undecene-4-yl ester (10d). To a 1.0 M
solution of undec-1-ene-4-ol (579 mg, 3.4 mmol) in CH2Cl2
was added Ac2O (0.7 mL, 6.8 mmol), and pyridine (0.6 mL,
7 mmol) at 0 8C and the reaction mixture was stirred
overnight (convenience). The solvent was removed under
reduced pressure, and excess Ac2O, Py were removed under
high vacuum. Flash chromatography (5% EA/hexanes)
furnished 581 mg (75%) of the acyl ester (w5 g scale,
1
78–80%). RfZ0.54 (5% EA/hex); H d 5.69 (ddt, 1H, JZ
17.1, 10.0, 7.0 Hz), 5.02 (broad dd, 1H, JZ17.0, 1.5 Hz),
4.99 (broad dd, 1H, JZ10.0, 0.8 Hz), 4.86 (m, 1H), 2.24 (m,
2H), 2.0 (s, 3H), 1.40 (2H), 1.25 (broad, 10H), 0.83 (t, 3H,
JZ7.0 Hz); 13C d 170.5, 133.7, 117.3, 73.2, 38.5, 33.5, 31.7,
29.3, 29.1, 25.3, 22.5, 21.0, 13.9; IR 1739, 1641; HRFAB
calcd for C13H24OLi (MCLi)C: 219.1936, found: 219.1186
(88 ppm).
4.2. Preparation of homoallyl ethers and esters (10a–10i)
Compounds 10a–i were prepared by etherification or
esterification of the corresponding homoallyl alcohol.17
4.2.1. 4-(tert-Butyldimethylsilyloxy)-1-methoxy-1-unde-
1
cene (10a).18 RfZ0.76 (5% EtOAc/Hex); H d 5.90 (d,
4.2.5. Benzoic acid, undecene-4-yl ester (10e). To a 1.0 M
solution of undec-1-ene-4-ol (740 mg, 4.3 mmol) in
CH2Cl2/Py (1:3) was added benzoyl chloride (1.5 mL,
13 mmol). The reaction mixture turns pink after the addition
of reagents is complete. After 1 h the reaction mixture is
quenched with sat. NH4Cl at 0 8C and extracted with 30%
recycled EA/hexanes (3!50 mL). The organics were dried
1H, 6.3), 4.39 (dd, 1H, JZ7.2, 13.6 Hz), 3.65 (m, 1H), 3.55
(s, 3H), 2.23–2.19 (2H), 1.27–1.44 (12H), 0.88–0.90 (12H),
0.05 (6H); 13C d 147.0, 103.0, 72.2, 59.3, 36.8, 31.8, 31.7,
29.7, 29.3, 25.9, 25.4, 22.7, 14.1, K4.4, K4.6; IR 1667,
1251, 1108; HRMS calcd for C18H37O2Si (MKH)C:
313.2562, found: 313.2556 (2.1 ppm).

A. Ahmed, P. H. Dussault / Tetrahedron 61 (2005) 4657–4670
4663
over Na2SO4. The solvent was removed under reduced
pressure and flash chromatography of the crude product
(10% EA/hexanes) furnished 1.1 g (90%) of the benzoyl
ester. RfZ0.68 (10% EA/hex); 1H (400 MHz) d 8.05 (broad
d, 2H, JZ7.6 Hz), 7.55 (dt, 1H, JZ7.3, 1.3 Hz), 7.43 (broad
t, 2H, JZ7.3 Hz) 5.83 (ddt, 1H, JZ17.2, 10.4, 7.0 Hz),
5.20–5.15 (m, 1H), 5.11 (dd, 1H, JZ17.2, 1.5 Hz), 5.06 (dd,
1H, JZ10.4, 1.7 Hz), 2.45 (t, 2H, JZ6.6 Hz), 1.76–1.61
(2H), 1.43–1.25 (10H), 0.87 (t, 3H, JZ6.8 Hz); 13C
(100 MHz) d 166.2, 133.7, 132.7, 130.7, 129.5, 128.3,
117.7, 74.0, 38.7, 33.6, 31.7, 29.4, 29.1, 25.3, 22.6, 14.0; IR
1719, 1643; HRFAB calcd for C18H26O2Li (MCLi)C:
281.2093; found: 281.2095 (0.7 ppm).
Na2SO4. The solvent was removed under reduced pressure.
Distillation of the crude product furnished 2-methyl-1-
decene-4-ol in (5.6 g, 75%) yield. Acylation of the alcohol
by a similar procedure as employed for the preparation of
compound 10d furnished the desired acetate ester in 62%
1
yield. RfZ0.74 (5% EA/hex); H d 5.02 (m, 1H), 4.74 (d,
1H, JZ6.3 Hz), 4.67 (d, 1H, JZ6.3 Hz), 2.27–2.14 (2H),
1.98 (s, 3H), 1.72 (s, 3H), 1.49 (2H), 1.24 (broad, 8H), 0.85
(t, 3H, JZ6.9 Hz); 13C d 170.5, 141.8, 113.0, 72.1, 42.9,
34.0, 31.7, 29.0, 25.3, 22.5, 22.4, 21.0, 13.9; IR 1735, 1643;
HR-EI calcd for C11H19 (MKAcOH)C: 152.1643; found:
152.1571 (47 ppm).
4.3. Ozonolysis of homoallyl ethers/esters (illustrated for
11d)
4.2.6. 4-(Methoxymethoxy)-undec-1-ene (10g). To a
1.0 M solution of undec-1-ene-4-ol (1.6 g, 9.2 mmol) in
DIPEA/CH2Cl2 (1:1) was added chloromethyl methyl ether
(1.4 mL, 18 mmol) at 0 8C and the reaction mixture was
stirred overnight (convenience). The reaction mixture was
quenched with satd NH4Cl at 0 8C and the aqueous layer
was extracted with recycled 20% EA/hexanes (3!25 mL).
The combined organics were dried over Na2SO4 and the
solvent was removed under reduced pressure. Flash
chromatography (5% EA/hexanes) of the crude product
furnished 1.51 g (75%) of the methoxymethyl ether. RfZ
0.39 (5% EA/hex); 1H d 5.76 (ddt, 1H, JZ17.0, 10.1,
6.9 Hz), 5.0 (dd, 1H, JZ17.3, 1.9 Hz), 4.97 (dd, 1H, JZ
10.1, 1.9 Hz), 4.5 (dd, 2H, JZ12.9, 6.9 Hz), 3.54 (m, 1H),
3.31 (s, 3H), 2.23 (broad t, 2H, JZ6.6 Hz), 1.45–1.23
(12H), 0.83 (t, 3H, JZ6.9 Hz); 13C d 135.0, 116.7, 95.5,
76.8, 55.3, 39.0, 34.3, 31.8, 29.7, 29.3, 25.3, 22.6, 13.9; IR
1646, 1149, 1099; HREI calcd for C10H21O2 (MKallyl)C:
173.1542, found: 173.1547 (2.8 ppm).
Into a K78 8C solution of alkene 10d (4.70 g, 20.6 mmol) in
2-methoxyethanol (100 mL, excess) tinted slightly pink
with a trace of Sudan Red B was bubbled a gaseous solution
of O3/O2. After the reddish color had faded to light yellow
and TLC analysis displayed little or no starting material,
ozonolysis was stopped and residual ozone was removed by
sparging with O2 or N2. The reaction mixture was allowed to
warm to room temperature and was diluted with DI water
(100 mL). The organic extracts (recycled EA/hex, 3!
100 mL), were dried over Na2SO4 and the solution was
concentrated in vacuo. Residual methoxyethanol was
removed under high vacuum, and the residue was purified
by flash chromatography (20% EA/hex) to furnish 3.7 g
(59%) of hydroperoxy acetal 11d. Compounds 11a–i were
prepared by a similar procedure. Unless otherwise noted,
the hydroperoxyacetals were formed as approximately 1:1
mixtures of diastereomers.
4.3.1. 3-tert-Butyldimethylsilyloxy-1-hydroperoxy-1-(2-
methoxyethoxy)decane (11a). YieldZ1.8 g, 73%. RfZ
0.39 (10% EA/hex); H d 10.30 (s, 0.5H), 10.25 (s, 0.5H),
4.2.7. Acetic acid, 1-phenyl-3-buten-1-yl ester (10h). To a
1.0 M solution of benzaldehyde (10.6 g, 100 mmol), in THF
was added a 2.0 M solution of allylmagnesium chloride
(76 mL, 150 mmol) in THF at 0 8C. The color of the
reaction mixture changed from reddish brown to dark green
as the reaction progressed. After 24 h the reaction mixture
was quenched with sat. NH4Cl at 0 8C and extracted with
recycled 20% EA/hexanes (3!150 mL). The combined
organic layers were dried over Na2SO4 and the solvent
removed under reduced pressure. The crude product was
distilled under reduced pressure to furnish 6.9 g (46%) of
1-phenyl-3-butenol. A portion of the alcohol (4.5 g,
30.3 mmol) was acylated using a procedure similar to
compound 10d to furnish the acetate ester in 4.15 g (72%)
1
4.97–4.92 (1H), 3.85–3.78 (3H), 3.66–3.60 (1H), 3.56–3.52
(1H), 3.43 (s, JZ1.6 Hz), 3.42 (s, 1.4H), 1.97–1.89 (2H),
1.83–1.79 (2H), 1.46–1.41 (2H), 1.29–1.24 (8H), 0.87 (s,
5H), 0.86 (s, 4H), 0.86–0.87 (3H), 0.05 (s, 1.4H), 0.04 (s,
1.4H), 0.38 (s, 3.2H); 13C d 105.1, 105.0, 72.9, 72.8, 69.0,
68.9, 65.4, 65.3, 58.6, 38.7, 38.4, 37.62, 37.59, 31.8, 31.7,
29.72, 29.68, 29.2, 25.9, 25.8, 24.7, 22.6, 18.01, 18.0, 14.0,
K4.3, K4.4, K4.6, K4.7; IR 3428, 2857–2848, 1255,
1102–1124; HRMS: no identifiable ions were observed.
4.3.2.
(1-Hydroperoxy)-3-methoxy-1-(2-methoxy-
1
yield. RfZ0.5 (4% EA/hex); H d 7.48–7.25 (5H), 5.80 (t,
ethoxy)-decane (11b). YieldZ204 mg, 45%. RfZ0.6
(40% EA/hex); 1H d 10.31 (s, 0.6H), 10.27 (s, 0.3H),
4.97–4.93 (m, 1H), 3.87–3.77 (m, 1H), 3.64–3.59 (2H),
3.56–3.49 (2H), 3.41 (s, 1.2H), 3.40 (s, 1.8H), 3.30 (s, 1.2H),
3.29 (s, 1.8H), 1.96–1.23 (m, 14H), 0.83 (t, 3H, JZ6.3 Hz);
13C d 105.1, 104.8, 77.5, 77.4, 72.7, 72.5, 65.7, 65.5, 58.9,
58.8, 56.7, 56.4, 35.9, 35.8, 33.3, 33.0, 31.7, 29.6, 29.1,
24.7, 22.5, 14.0; IR 3331, 1198, 1104; HRMS: no
identifiable ions were observed.
1H, JZ6.3 Hz), 5.69 (ddt, 1H, JZ17.3, 10.4, 6.9 Hz), 5.05
(dd, 1H, JZ17.9, 1.9 Hz), 5.03 (dd, 1H, JZ10.1, 1.6 Hz),
2.67–2.52 (m, 2H), 2.03 (s, 3H); 13C d 170.0, 140.0, 133.2,
128.3, 127.8, 126.4, 117.8, 75.0, 40.6, 21.0; IR 1748, 1637,
1492, 1458, 1424; HRFAB calcd for C12H14O2Li (MC
Li)C: 197.1154, found: 197.115 (0.9 ppm).
4.2.8. Acetic acid, 2-methyl-1-undecene-4-yl ester (10i).
To a 1.0 M solution of heptanal (5 g, 43.8 mmol) in THF
was added a solution of methallyl magnesium bromide
(1.1 equiv) in THF at 0 8C. After 24 h stirring the reaction
mixture was quenched with satd NH4Cl and the aqueous
layer was extracted with recycled 20% EA/hexanes. The
organics were washed with water and brine and dried over
4.3.3. 3-Benzyloxy-1-hydroperoxy-1-(2-methoxyethoxy)-
decane (11c). YieldZ300 mg, 50%. RfZ0.45 (20% EA/
hex); 1H d 10.27 (s, 0.8H), 9.73 (t, 0.2H, JZ1.9 Hz), 7.35–
7.24 (5H), 5.05–5.02 (m, 0.4H), 4.99 (broad t, 0.6H, JZ
6.0 Hz), 4.60–4.50 (2H), 3.86–3.78 (m, 0.7H), 3.72–3.68

4664
A. Ahmed, P. H. Dussault / Tetrahedron 61 (2005) 4657–4670
(m, 0.3H), 3.65–3.57 (m, 2H), 3.56–3.45 (m, 2H), 3.43 (s,
1.2H), 3.42 (s, 1.8H), 2.40 (m, 0.4H), 2.05–1.79 (m, 1.6H),
1.65–1.27 (12H), 0.89 (t, 3H, JZ6.9 Hz); 13C d 138.7,
128.3, 128.24/128.22, 127.77, 127.73, 127.66, 127.51,
127.48, 127.43, 127.41, 127.38, 105.2, 105.0, 75.9, 75.7,
72.8, 72.7, 72.6, 71.3, 70.9, 69.9, 65.9, 58.8, 43.7, 36.3,
34.9, 33.9, 31.7, 29.64/29.62, 29.4, 29.1, 25.8, 24.9, 24.8,
22.5, 21.8, 14.0; IR 3331, 1495, 1451, 1198, 1096; HRMS:
no identifiable ions were observed.
4.3.8. Acetic acid, 1-hydroperoxy-1-(2-methoxyethoxy)-
3-phenyl propane-3-yl ester (11h). YieldZ2.8 g, 50%.
RfZ0.44 (40% EA/hex); 1H d 10.53 (s, 1H), 7.53–7.40
(5H), 6.07–5.99 (1H), 4.97–4.95 (0.7H), 4.88 (t, 0.3H, JZ
6.0 Hz), 3.96–3.92 (2H), 3.79–3.70 (2H), 3.56 (s, 1H), 3.55
(s, 2H), 2.16 (s, 3H), 1.85–1.43 (2H); 13C d 169.9, 140.0,
128.4, 128.0, 126.42, 126.38, 104.37, 104.0, 72.65, 72.63,
72.57, 72.54, 72.4, 66.2, 58.8, 38.3, 37.9, 21.0; IR 3330 (b),
1740, 1490, 1600, 1124; HRMS: no identifiable ions were
observed.
4.3.4. Acetic acid, 1-hydroperoxy-1-(2-methoxyethoxy)
decane-3-yl ester (11d). YieldZ2.9 g, 60%. RfZ0.39
(20% EA/hex); H d 10.33 (s, 0.8H), 10.23 (s, 0.2H), 4.94
4.3.9. Acetic acid, 2-hydroperoxy-2-methoxyethoxy-
decane-4-yl ester (11i). YieldZ493 mg, 62%. RfZ0.64
(40% EA/hex); 1H d 10.14 (s, 0.6H), 10.10 (s, 0.4H), 5.0 (m,
1H), 3.50–3.41 (4H), 3.329 (s, 1.3H), 3.326 (s, 1.7H), 1.98
(s, 1H), 1.90 (s, 2H), 1.88–1.87 (1H), 1.45–1.14 (m, 3H),
1.24 (s, 1.8H), 1.22 (s, 1.2H), 1.18–1.15 (8H), 0.76 (t, 3H,
JZ7.0 Hz); 13C d 170.4, 170.2, 105.7, 105.5, 72.6, 70.5,
70.3, 59.8, 59.7, 58.6, 39.64, 39.59, 35.1, 35.0, 31.4, 28.8,
24.7, 22.3, 21.03, 21.0, 19.6, 19.4, 13.8; IR 3308, 1734,
1125; HRMS: no identifiable ions were observed.
1
(m, 1H), 4.79 (m, 1H), 3.94–3.83 (m, 2H), 3.72–3.59 (m,
2H), 3.50 (s, 1.8H), 3.49 (s, 1.2H), 2.09 (s, 1.8H), 2.08 (s,
1.2H), 1.99–1.94 (m, 2H), 1.62–1.60 (m, 2H), 1.31 (broad s,
10H), 0.92 (t, 3H, JZ6.6 Hz); 13C d 170.5/170.4, 104.8/
104.5, 72.5/72.4, 71.7/71.6, 66.5, 65.4, 58.7, 36.3, 35.9,
34.4, 34.1, 31.5, 31.0, 29.1, 28.9, 28.3, 24.9, 24.86, 22.4,
20.93, 20.9, 13.8; IR 3300 (b), 1734, 1124, 1100; HRMS: no
identifiable ions were observed.
4.3.5. Benzoic acid, 1-hydroperoxy-1-(2-methoxyethoxy)
decane-3-yl ester (11e). YieldZ510 mg, 40%. RfZ0.47
(20% EA/hex); H d 10.46 (s, 0.6H), 10.30 (s, 0.4H), 8.0
4.4. Silylation of hydroperoxyacetals (illustrated for 12d)
1
Into a 0 8C solution of hydroperoxyacetal 11d (3.70 g,
12.0 mmol) in DMF (15 mL) under N2, was added
imidazole (1.5 equiv, 1.22 g, 18 mmol) followed by
TBSOTf (18 mmol, 4.2 mL, dropwise). The reaction was
stirred for 25–30 min and then quenched with DI water
(50 mL). The combined organic extracts (recycled EA/
hexane, 3!100 mL) were dried over Na2SO4, and the
solvent removed in vacuo. The crude product was purified
by flash chromatography (10% EA/hex) to furnish 4.5 g
(88%) of the silyl peroxyacetal 12d. Compounds 12a–i were
prepared by similar procedures.
(broad d, 2H, JZ7.9 Hz), 7.53–7.51 (1H), 7.41 (broad t, 2H,
JZ7.6 Hz), 5.31–5.25 (m, 1H), 4.96 (t, 0.5H, JZ6.0 Hz),
4.93 (t, 0.5H, JZ6.0 Hz), 3.8–3.7 (2H), 3.66–3.62
(2H), 3.40 (s, 1.8,H), 3.38 (s, 1.2H), 2.16–2.02 (2H),
1.76–1.61 (4H), 1.39–1.22 (8H), 0.83 (broad t, 3H, JZ
6.3 Hz); 13C d 166.0, 132.8, 132.7, 130.5, 130.3, 129.5,
129.4, 128.25, 128.2, 104.8, 104.5, 72.6, 72.5, 71.6, 66.5,
65.3, 58.83, 58.76, 36.4, 36.1, 34.6, 34.3, 31.6, 29.3, 29.0,
25.01, 24.99, 22.5, 13.9; IR 3315 (b), 1719, 1581, 1450,
1192, 1102, 1071; HRMS: no identifiable ions were
observed.
4.4.1. 1-(tert-Butyldimethylsilyldioxy)-3-(tert-butyldi-
methylsilyloxy)-1-(2-methoxyethoxy)-decane (12a).
YieldZ427 mg, 85%. RfZ0.65 (10% EA/hex); 1H d
4.99–4.94 (1H), 4.10–4.05 (0.5H), 4.02–3.98 (0.5H), 3.83–
3.71 (2H), 3.59–3.49 (2H), 3.36 (s, 1.6H), 3.356 (s, 1.4H),
1.89–1.68 (2H), 1.43 (broad peak, 2H), 1.25 (broad peak,
12H), 0.92 (s, 9H), 0.87 (s, 9H), 0.88–0.85 (3H), 0.15
(s, 6H), 0.05 (s, 1.6H), 0.04 (4.4H); 13C d 106.5, 105.9,
72.1, 72.0, 69.2, 69.0, 68.9, 68.7, 58.9, 58.87, 39.8, 39.5,
37.6, 37.5, 31.79, 31.78, 29.7, 29.2, 26.12, 26.1, 25.8,
24.9, 24.7, 22.6, 18.1, 18.01, 18.0, 14.0, K4.3, K4.4, K4.6,
K4.6, K5.7; IR 2959–2851, 1101, 1252, 1203; HRMS: no
identifiable ions were observed.
4.3.6. 2,2-Dimethylpropionic acid, 1-hydroperoxy-1-(2-
methoxyethoxy) decane-3-yl ester (11f). The title com-
pound was prepared by esterification of undecen-4-ol
followed by ozonolysis of the crude pivaloate ester in
1
325 mg, 50% yield. RfZ0.26 (20% EA/hex); H d 10.38
(0.4H), 10.25 (0.6H), 5.04–4.92 (1H), 4.88 (t, 0.6H, JZ
6.0 Hz), 4.83 (t, 0.4H, JZ5.7 Hz), 3.86–3.78 (2H), 3.67–
3.51 (2H), 3.425 (s, 1.8H), 3.429 (s, 1.2H), 1.93–1.85 (2H),
1.67–1.55 (4H), 1.179 (s, 3.6H), 1.173 (s, 5.4H), 1.17–1.50
(8H), 0.85 (t, 3H, JZ6.9 Hz); 13C d 178.0/177.9, 105.1,
104.7, 72.8, 72.7, 70.7, 70.6, 70.3, 70.2, 66.6, 65.2, 63.5,
58.9, 58.87, 58.83, 39.2, 38.8, 38.76, 36.5, 36.1, 34.5, 34.2,
33.9, 31.7, 29.3, 29.2, 29.1, 27.16, 27.13, 27.0, 24.97, 24.94,
22.5, 13.1; IR 1725, 1159, 1130, 1101; HRMS: no
identifiable ions were observed.
4.4.2. 1-(tert-Butyldimethylsilyldioxy)-3-methoxy-1-(2-
methoxyethoxy) decane (12b). YieldZ135 mg, 87%.
RfZ0.68 (20% EA/hex); 1H d 5.02 (m, 1H), 4.10–4.03
(m, 1H), 3.83–3.75 (m, 2H), 3.61–3.51 (2H), 3.38 (s, 1.7H),
3.37 (s, 1.3H), 3.32 (s, 3H), 1.87–1.66 (m, 2H), 1.50–1.25
(12H), 0.92 (s, 3.8H), 0.91 (s, 5.2H), 0.85 (t, 3H, JZ
6.6 Hz), 0.26 (s, 3.4H), 0.16 (s, 2.6H); 13C d 106.4/106.1,
77.4, 72.1, 72.0, 69.4, 69.0, 58.82, 58.78, 56.3, 37.0, 33.7,
33.6, 31.8, 29.75, 29.68, 29.2, 26.1, 25.7, 25.6, 24.9, 22.6,
18.1, 14.0, K3.0, K5.7; IR 2962–2851, 1249, 1199, 1095;
HRFAB calcd for C20H44O5SiLi (MCLi)C: 399.3118;
found: 399.3125 (1.6 ppm).
4.3.7. 1-(2-Ethoxymethoxy)-3-(methoxymethoxy)decyl
hydroperoxide (11g). YieldZ0.8 g, 55%. RfZ0.39 (20%
EA/hex); 1H d 10.27 (s, 1H), 4.90 (s, 0.1H), 4.77 (t, 1H, JZ
6 Hz), 4.52 (s, 1.9H), 3.77–3.75 (1H), 3.57–3.47 (2H), 3.43
(t, 2H, JZ6.3 Hz), 3.37 (s, 3H), 3.30 (s, JZ0.3 Hz), 3.27 (s,
2.7H), 1.68–1.28 (17H); 13C d 107.2, 99.0, 96.3, 77.2, 72.6,
72.3, 67.0, 67.5, 65.3, 58.7, 54.8, 31.1, 29.4, 28.3, 25.5 25.8,
24.4, 24.2, 12.0; IR 3316, 1196, 1102, 1044; HRMS: no
identifiable ions were observed.

A. Ahmed, P. H. Dussault / Tetrahedron 61 (2005) 4657–4670
4665
4.4.3. 1-(tert-Butyldimethylsilyldioxy)-3-benzyloxy-1-(2-
methoxyethoxy)-decane (12c). YieldZ2.8 g, 88%. RfZ
0.71 (20% EA/hex); H d 7.37–7.27 (5H), 5.14–5.07 (1H),
4.73 Hz), 3.99 (m, 1H), 3.78–3.70 (2H), 3.52–3.42 (2H),
3.30 (s, 3H), 3.27 (s, 3H), 1.59–1.49 (6H), 1.40–1.30 (8H),
0.86 (s, 9H), 0.83 (broad t, 3H, JZ6.6 Hz), 0.10 (s, 6H);
13C d 108.2, 99.7, 96.2, 72.0, 71.7, 69.1, 68.7, 67.4, 58.8,
58.7, 54.8, 32.1, 30.1, 29.4, 26.0, 25.8, 24.4, 17.9, K5.8,
K6.0; IR 1111, 1045; HRMS: no identifiable ions were
observed.
1
4.50–4.49 (2H), 4.10–3.96 (1H), 3.65–3.46 (2H), 3.39–3.34
(2H), 3.36 (s, 3H), 1.95–1.78 (2H), 1.63–1.50 (2H), 1.48–
1.3 (10H), 0.97 (s, 4.6H), 0.969 (s, 4.4H), 0.92 (t, 3H, JZ
6.6 Hz), 0.19 (s, 2.7H), 0.18 (s, 3.3H); 13C d 139.0, 138.97,
128.2, 128.1, 127.6, 127.58, 127.5, 127.46, 127.43, 127.3,
127.26, 106.3, 106.0, 75.8, 75.7, 72.8, 72.0, 70.9, 70.8, 69.4,
38.9, 58.73, 58.69, 37.35, 37.26, 34.1, 34.0, 31.7, 29.7, 29.6,
29.1, 26.1, 25.7, 25.0, 24.9, 22.5, 18.05, 18.03, 13.9, K4.1,
K4.2, K5.73, K5.7; IR 2962–2855, 1494, 1462, 1249,
1106; HRFAB calcd for C26H48O5SiNa (MCNa)C:
491.3171; found: 491.3151 (3.6 ppm).
4.4.8. Acetic acid, 1-(tert-butyldimethylsilyldioxy)-3-phe-
nyl-1-(2-methoxyethoxy)-decane-3-yl ester (12h).
YieldZ2.0 g, 55%. RfZ0.5 (20% EA/hex); 1H d 7.49–
7.17 (5H), 5.91–5.85 (1H), 4.96–4.94 (0.8H), 4.81 (t, 0.2H,
JZ6.0 Hz), 4.07–3.70 (2H), 3.71–3.49 (2H), 3.38 (s, 1.2H),
3.36 (s, 1.8H), 2.36–2.33 (m, 2H), 2.03 (s, 1.8H), 2.02
(s, 1.2H), 0.94 (5.6H), 0.93 (3.4H), 0.18 (s, 3.4H), 0.17
(s, 2.6H); 13C d 169.66, 169.62, 140.3, 140.1, 128.39,
128.36, 127.9, 127.8, 126.4, 126.3, 105.3, 105.1, 72.7,
72.66, 72.0, 71.8, 69.5, 68.8, 58.8, 58.7, 39.1, 38.8, 26.03,
26.0, 25.6, 21.0, 20.96, 18.0, 17.8, K3.7, K5.8; IR 2930–
2848, 1741, 1464, 1366, 1230, 1116; HRFAB calcd for
C20H34O6SiNa (MCNa)C: 421.2025, found: 421.2036
(2.6 ppm).
4.4.4. Acetic acid, 1-(tert-butyldimethylsilyldioxy)-1-(2-
methoxyethoxy)-decane-3-yl ester (12d). YieldZ4.5 g,
88%. RfZ0.42 (10% EA/hex); 1H d 5.0 (m, 1H), 3.99–3.96
(m, 1H), 3.74–3.68 (2H), 3.54–3.47 (2H), 3.46 (s, 1.2H),
3.45 (s, 1.8H), 2.0 (s, 1.8H), 1.99 (s, 1.2H), 1.95–1.76 (4H),
1.60–1.40 (broad peak, 2H), 1.15–1.30 (8H), 0.9 (s, 6.7H),
0.89 (s, 2.3H), 0.83 (t, 3H, JZ6 Hz), 0.125 (s, 4H), 0.11 (s,
1.9H). 13C d 170.24/170.21, 105.9/105.5, 72.0/71.97, 71.1/
71.0, 69.76/68.74, 58.78/58.71, 37.0, 36.8, 34.5, 34.2, 31.6,
29.3, 29.0, 26.04, 26.02, 25.7, 25.6, 25.0, 22.5, 21.1, 21.0,
18.0, 13.9, K5.8; IR 2928–2850, 1734, 1233, 1130, 1101;
HRMS: no identifiable ions were observed.
4.4.9. Acetic acid, 2-(tert-butyldimethylsilyldioxy)-2-(2-
methoxyethoxy)-nonane-4-yl ester (12i). YieldZ584 mg,
1
75%. RfZ0.65 (20% EA/hex); H d 5.03 (m, 1H), 3.59
(broad t, 2H, JZ5.0 Hz), 3.47 (broad t, 2H, JZ5 Hz), 3.30
(s, 3H), 1.95 (s, 3H), 2.08–2.04 (1.2H), 1.78–1.74 (0.8H),
1.53–1.49 (3H), 1.29 (s, Me, 1.4H), 1.27 (s, Me, 1.6H), 1.21
(broad peak, 7H), 0.88 (s, 9H), 0.81 (t, 3H, JZ6.3 Hz), 0.10
(s, 1.5H), 0.08 (s, 4.5H); 13C d 170.2, 170.1, 105.6, 105.4,
71.9, 71.8, 71.1, 70.6, 60.9, 60.4, 58.8, 40.4, 40.3, 35.5,
35.2, 31.6, 29.1, 29.0, 26.05, 26.03, 24.95, 24.87, 22.4, 21.2,
21.1, 20.4, 19.8, 18.15, 18.11, 13.9, K5.8; IR 2928–2855,
1739, 1247, 1130; HRFAB calcd for C21H44O6SiNa (MC
Na)C: 443.2807; found: 443.2822 (3.3 ppm).
4.4.5. Benzoic acid, 1-(tert-butyldimethylsilyldioxy)-1-(2-
methoxyethoxy)-decane-3-yl ester (12e). YieldZ291 mg,
1
75%. RfZ0.5 (10% EA/hex); H d 8.03 (broad d, 2H, JZ
8.2 Hz), 7.55–7.51 (m, 1H), 7.43–7.40 (m, 2H), 5.31–5.21
(m, 0.4H), 5.03–4.96 (m, 0.6H), 4.06 (broad t, 1H, JZ
5.0 Hz), 3.76–3.70 (m, 2H), 3.52–3.42 (m, 2H), 3.30 (s, 1H),
3.29 (s, 2H), 2.02–1.98 (m, 2H), 1.75–1.64 (m, 2H), 1.40–
1.20 (m, 10H), 0.91 (s, 9H), 0.84 (broad t, 3H, JZ6 Hz),
0.16 (s, 3.9H), 0.13 (s, 2.1H); 13C d 165.8, 165.78, 132.7,
132.6, 130.6, 130.5, 129.5, 128.23, 128.19, 105.9, 105.4,
72.0, 71.9, 71.8, 71.7, 69.9, 68.7, 58.8, 58.7, 37.1, 36.8,
34.6, 34.3, 31.7, 29.36, 29.32, 29.0, 26.0, 24.99, 24.97, 22.5,
18.04, 18.02, 14.0, K5.8; IR 2859–2849, 1710, 1601, 1580,
1462, 1441, 1275, 1175, 1106, 1023; HRFAB calcd for
C26H46O6SiLi (MCLi)C: 489.3224; found: 489.3243
(3.9 ppm).
4.4.10. Undecene-5-ol.19 The title compound was prepared
by a reported procedure.
4.4.11. 5-Methoxyundecene (13a). The title compound was
prepared using a reported procedure7. YieldZ1.3 g, 75%.
1
RfZ0.2 (2% EA/hex); H d 5.82 (ddt, 1H, JZ17.0, 10.4,
6.6 Hz), 5.01 (broad dd, 1H, JZ17.0, 1.9 Hz), 4.98 (dd, 1H,
JZ10.1, 1.9 Hz), 3.31 (s, 3H), 3.14 (m 1H), 2.19–2.01 (2H),
1.69–1.21 (12H), 0.88 (t, 3H, JZ6.9 Hz); 13C d 138.8,
114.3, 80.3, 56.4, 33.5, 32.85, 29.6, 29.5, 25.2, 22.6, 14.0;
IR 1633, 1103, 1158; HREI calcd for C12H25O (MCH)C:
185.1905; found: 185.1896 (4.8 ppm).
4.4.6. 2,2-Dimethylpropionic acid, 1-(tert-butyldimethyl-
silyldioxy)-1-(2-methoxyethoxy)-decane-3-yl ester (12f).
1
YieldZ212 mg, 60%. RfZ0.72 (20% EA/hex); H d 5.03–
4.81 (m, 1H), 4.07–3.96 (1H), 3.75–3.68 (2H), 3.56–3.48
(2H), 3.35 (s, 1.2H), 3.33 (1.8H), 1.56–1.48 (2H), 1.28–1.20
(12H), 1.17 (s, 3.7H), 1.16 (s, 5.3H), 0.91 (s, 9H),
0.84 (broad t, 3H), 0.14 (s, 3.4H), 0.13 (s, 2.6H); 13C d
177.57, 177.55, 106.0, 105.4, 72.0, 71.9, 70.7, 70.68, 70.0,
68.6, 58.84, 58.80, 45.2, 38.73, 38.7, 37.1, 36.8, 34.5, 34.1,
31.7, 29.3, 29.1, 27.2, 27.1, 26.08, 26.06, 25.7, 25.6, 25.5,
24.8, 22.5, 18.07, 18.05, 14.0; IR 2953–2855, 1729, 1246,
1158, 1109; HRFAB calcd for C24H50O6SiLi (MCLi)C:
469.3537; found: 469.3541 (0.8 ppm).
4.4.12. 5-Iodoundecene (13b). Into a 0 8C solution of
undec-1-ene-5-ol (3.6 g, 21.1 mmol) in CH2Cl2 (50 mL)
were successively added PPh3 (6.1 g, 23.2 g), I2 (7.5 g,
29.5 mmol) and imidazole (2.0 g, 29.5 mmol). The reaction
was stirred overnight (convenience), diluted with CH2Cl2
(50 mL) and then quenched with DI water and washed with
aqueous sodium thiosulphate solution (3!100 mL). The
organic layer was dried over Na2SO4 and concentrated to
give a white solid which was washed with hexanes (3!
100 mL). The hexanes were removed under reduced
pressure to give a colorless liquid which was purified by
flash chromatography (10% EA/hex) to furnish the iodide
(5.2 g, 88%): RfZ0.88 (10% EA/hex); 1H (400 MHz) d 5.77
4.4.7.
1-(tert-Butyldimethylsilyldioxy)-3-methoxy-
methoxy-1-(2-methoxyethoxy)decane (12g). YieldZ
1
293 mg, 82%. RfZ0.6 (20% EA/hex); H d 4.97 (s, 0.1H),
4.80 (t, 0.9H, JZ5.7 Hz), 4.53 (s, 1.9H), 4.15 (t, 0.1H, JZ

4666
A. Ahmed, P. H. Dussault / Tetrahedron 61 (2005) 4657–4670
(ddt, 1H, JZ17.2, 10.4, 6.8 Hz), 5.07 (broad dd, 1H, JZ
17.2, 1.5 Hz), 5.0 (broad dd, 1H, JZ10.4, 1.8 Hz), 4.1 (m,
1H), 2.34–2.12 (2H), 2.0–1.65 (4H), 1.56–1.28 (8H), 0.88 (t,
3H, JZ6.8 Hz); 13C (100 MHz) d 137.0, 115.6, 40.6, 39.6,
39.4, 33.6, 31.6, 29.4, 28.5, 22.6, 14.0; IR 1636, 1300, 1225,
1151; HREI calcd for C11H21I (M)C: 280.0688; found:
280.0685 (1.0 ppm).
0.35 mmol) and allylsilane (2.0 equiv, 0.7 mmol, 0.1 mL) in
CH2Cl2 (4 mL) under N2, was added a solution of SnCl4 in
CH2Cl2, (nominally 1.0 M solution, 0.4 mL, dropwise). The
reaction mixture was allowed to stir for 1hr, and then
quenched with DI water. The organic extracts (50%
recycled EA/hex, 3!15 mL) were dried over Na2SO4,
and solvent was removed under reduced pressure. Flash
chromatography (5% EA/hex) furnished 95 mg (60%) of
the allylated peroxide (15d). Compounds 15a–f, 16, 17, 19
and 21 were prepared similarly.
4.4.13. [1-tert-Butyldimethylsilyldioxy]-4-methoxy-1-(2-
methoxyethoxy) decane (14a). Ozonolysis of 5-methoxy-
undecene in 2-methoxyethanol furnished 4-methoxy-1-(2-
methoxyethoxy)-dec-1-yl-hydroperoxide in 307 mg, 50%
yield: RfZ0.33 (20% EA/hex); 1H d 10.32 (s, 0.6H), 10.30
(0.4H), 4.81 (t, 1H, JZ6.0 Hz), 3.83–3.76 (2H), 3.62–3.58
(1H), 3.55–3.51 (1H), 3.41 (s, 3.0H), 3.274 (s, 1.5H), 3.271
(s, 1.5H), 3.15–3.09 (m, 1H), 1.79–1.24 (14H), 0.84 (t, 3H,
JZ6.3 Hz); 13C d 107.4, 80.4, 72.7, 65.3, 65.1, 58.8, 56.2,
56.1, 33.3, 31.7, 29.45, 29.38, 28.4, 28.2, 27.06, 25.15,
25.13, 22.5, 13.9; IR 3332, 1174, 1086; HRMS: no
identifiable ions were observed.
4.5.1. 4-(tert-Butyldimethylsilyldioxy)-6-(tert-butyldi-
methylsilyloxy)-1-tridecene (15a). YieldZ63 mg, 65%.
RfZ0.82 (5% EA/hex); 1H d 5.82 (m, 1H), 5.08 (dd, 1H, JZ
17.0, 1.9 Hz), 5.04 (dd, 1H, JZ9.1, 1.9 Hz), 4.10–4.01 (m,
1H), 3.85–3.76 (m, 1H), 2.55–2.25 (2H), 1.80–1.27 (broad,
17H), 0.94 (s, 5.4H), 0.93 (s, 3.6H), 0.88 (s, 9H), 0.15 (s,
6H), 0.06 (s, 2.8H), 0.05 (s, 3.2H); 13C d 135.0/134.7, 116.9,
116.7, 81.94, 81.87, 69.8, 69.6, 39.7, 38.2, 37.8, 37.4, 37.0,
31.9, 29.8, 29.3, 26.2, 26.0, 25.96, 25.2, 24.9, 22.6, 18.2,
18.1, 14.0, 12.2, K4.2, K4.37, K4.41, K5.58, K5.61; IR
2962–2851, 1641, 1249; HRMS: no identifiable ions were
observed.
Silylation of the hydroperoxyacetal under standard con-
ditions furnished silyl peroxyacetal 14a in 268 mg, 87%
yield: RfZ0.68 (20% EA/hex); 1H d 4.81 (broad t, 1H, JZ
5.7 Hz), 4.0–3.96 (m, 1H), 3.74–3.69 (m, 1H), 3.51–3.43
(m, 2H), 3.29 (s, 3H), 3.22 (s, 3H), 3.06 (m, 1H), 1.70–1.20
(14H), 0.87 (s, 9H), 0.8 (t, 3H, JZ6.0 Hz), 0.10 (s, 3H), 0.09
(s, 3H); 13C d 108.41, 108.36, 80.4, 80.2, 72.1, 69.1, 69.0,
58.7, 56.1, 33.3, 33.2, 31.7, 29.3, 28.2, 28.1, 28.0, 27.9,
26.0, 25.0, 22.4, 17.9, 13.8, K5.8; IR 2955–2819, 1198,
1247, 1106; HRFAB calcd for C20H44O5SiLi: (MCLi):
399.3118; found: 399.3132 (3.6 ppm).
4.5.2. 4-(tert-Butyldimethylsilyldioxy)-6-methoxy-1-tri-
decene (15b). YieldZ61 mg, 60%. RfZ0.64 (5% EA/
hex); 1H d 5.82 (ddt, 1H, JZ17.3, 10.1, 6.9 Hz), 5.07 (broad
dd, 1H, JZ15.1, 1.9 Hz), 5.04 (broad dd, 1H, JZ10.4,
1.6 Hz), 4.16–4.11 (m, 1H), 4.06–4.01 (m, 1H), 3.33 (s,
0.9H), 3.29 (s, 2.1H), 2.53–2.28 (m, 2H), 1.88 (m, 0.3H),
1.68–1.58 (m, 1.7H), 1.54–1.27 (12H), 0.94 (s, 9H), 0.88
(t, 3H, JZ6.9 Hz), 0.16 (s, 1.4H), 0.15 (s, 4.5H); 13C d
134.8/134.6, 117.04/117.01, 81.9, 78.0, 56.0, 37.7, 37.2,
35.8, 35.7, 33.8, 31.8, 29.8, 29.3, 26.2, 25.2, 25.0, 22.6,
18.2, 14.0, 14.02, K5.6; IR 2948–2854, 1635, 1246, 1130;
HRMS: no identifiable ions were observed.
4.4.14. [1-tert-Butyldimethylsilyldioxy]-4-iodo-1-(2-
methoxyethoxy)-decane (14b). Ozonolysis of iodo-
undecene in 2-methoxyethanol furnished 4-iodo-1-(2-meth-
oxyethoxy)-dec-1-yl-hydroperoxide in 1.7 g, 45% yield:
1
RfZ0.42 (20% EA/hex); H d 10.36 (s, 0.5H), 10.33 (s,
4.5.3. 6-Benzyloxy-4-(tert-butyldimethylsilyldioxy)-1-tri-
decene (15c). YieldZ60 mg, 50%. RfZ0.55 (5% EA/hex);
1H d 7.35–7.27 (5H), 5.85–5.77 (ddt, 1H, JZ17.0, 10.1,
6.9 Hz), 5.19 (dd, 1H, JZ17.0, 1.3 Hz), 5.15 (dd, 1H, JZ
10.4, 1.3 Hz), 4.50 (s, 1.2H), 4.49 (s, JZ0.8 Hz), 4.11–4.06
(m, 0.4H), 3.71–3.66 (m, 0.6H), 3.57–3.53 (m, 0.4H), 3.47
(m, 0.6H), 2.52–2.17 (2H), 1.75–1.28 (14H), 0.94 (s, 3.7H),
0.89 (s, 5.3H), 0.90–0.88 (3H, along with tert-Bu) 0.05 (s,
3.6H), 0.049 (s, 2.4H); 13C d 139.0, 138.7, 135.4, 134.7,
134.6, 128.3, 128.7, 127.7, 127.6, 127.5, 127.43, 127.37,
117.1, 116.9, 116.5, 81.9, 76.5, 76.0, 72.9, 72.0, 71.2, 70.4,
41.9, 37.7, 37.5, 37.2, 36.7, 36.2, 34.4, 34.0, 31.8, 29.8,
29.7, 29.3, 26.3, 26.2, 25.9, 25.3, 25.2, 25.1, 22.6, 18.2,
18.1, 14.0, K1.0, K4.4, K4.5, K5.6; IR 2951–2848, 1638,
1502, 1469, 1247, 1209, 1095; HRMS: no identifiable ions
were observed.
0.5H), 4.83 (t, 0.8H, JZ6.31 Hz), 4.21 (t, 0.2H, JZ
4.73 Hz), 4.12–4.06 (m, 1H), 3.86–3.78 (2H), 3.65–3.53
(2H), 3.434 (s, JZ1.6 Hz), 3.431 (s, 1.4H), 1.87–1.63
(6H), 1.49–1.26 (8H), 0.86 (t, 3H, JZ6.9 Hz); 13C d
106.4, 106.3, 72.8, 70.4, 65.5, 65.23, 63.5, 58.9,
40.71, 40.68, 40.5, 38.9, 38.7, 38.0, 35.8, 35.6, 35.4,
34.2, 31.6, 31.3, 29.35, 29.32, 28.4, 22.5, 13.9; IR 3370 (b),
1371, 1192, 1084; HRMS: no identifiable ions were
observed.
Silylation of the hydroperoxyacetal furnished 14b in 1.3 g,
1
79% yield. RfZ0.36 (2% EA/hex); H d 4.89–4.86 (1H),
4.10–4.01 (2H), 3.77 (m, 1H), 3.57–3.49 (2H), 3.36 (s,
1.5H), 3.356 (s, JZ1.5 Hz), 1.92–1.62 (6H), 1.52–1.26
(8H), 0.92 (s, 9H), 0.86 (t, 3H, JZ6.9 Hz), 0.16 (s, 3H), 0.15
(s, 3H); 13C d 107.6, 107.5, 72.2, 69.4, 69.3, 58.9, 58.89,
40.65, 40.6, 38.99, 38.9, 35.64, 35.56, 32.5, 32.3, 31.6, 29.4,
28.4, 26.1, 25.7, 25.6, 22.5, 18.1, 14.0, K3.0, K5.7; IR
2949–2849 (several bands), 1356, 1202, 1102; HRFAB
calcd for C19H41IO4SiLi (MCLi)C: 495.1229; found:
495.1995 (3.2 ppm).
4.5.4. Acetic acid, 4-(tert-butyldimethylsilyldioxy)-1-tri-
decen-6-yl ester (15d). YieldZ95 mg, 65%. RfZ0.62 (5%
1
EA/hex); H d 5.78 (ddt, 1H, JZ17.0, 9.0, 7.0 Hz), 5.18–
4.99 (3H), 3.99–3.94 (m, 1H), 2.008 (s, 1.2H), 2.006 (s,
1.8H), 2.50–2.26 (m, 2H), 1.92–1.63 (m, 2H), 1.21 (broad,
12H), 0.92 (s, 3.2H). 0.91 (s, 5.8H), 0.83 (t, 3H, JZ6.9 Hz),
0.13 (s, 3.4H), 0.12 (s, 2.6H); 13C d 170.46/170.42, 134.3/
134.1, 117.4/117.2, 81.6/81.5, 71.9/71.5, 37.4, 36.7, 36.6,
36.0, 34.7, 34.3, 31.7, 34.3, 31.7, 29.4, 29.3, 29.1, 26.15,
4.5. Allylation of peroxyacetals (illustrated for 15d)
Into a 0 8C solution of silyl peroxy acetal 12d (171 mg,

A. Ahmed, P. H. Dussault / Tetrahedron 61 (2005) 4657–4670
4667
26.13, 25.9, 25.8, 25.7, 25.2, 25.0, 22.6, 21.2, 18.1, 14.0,
K5.72/-5.74; IR 2954–2853, 1736, 1640, 1232; HRFAB
calcd for C21H42O4SiLi (MCLi)C: 393.3012; found:
393.3009 (0.9 ppm).
4.5.9. 6-But-3-enyloxy-tridec-1-en-4-yl tert-butyl
dimethylsilyl peroxide (17). YieldZ52 mg, 40%. RfZ0.7
(10% EA/hex); H d 5.86–5.75 (ddt, 2H, JZ16.1, 10.4,
1
6.6 Hz), 5.08 (dd, 2H, JZ16.7, 1.9 Hz), 5.03 (dd, 2H, JZ
10.4, 1.6 Hz), 3.90 (m, 1H), 3.45 (t, 1H, JZ6.9 Hz), 3.40 (t,
1H, JZ6.6 Hz), 3.40–3.50 (1H), 2.47–2.25 (4H), 1.57–1.22
(14H), 0.93 (s, 9H), 0.89–0.88 (3H), 0.15 (s, 3.1H), 0.14
(2.9H); 13C d 135.3, 134.7, 116.2, 84.6, 70.8, 70.1, 36.8,
34.2, 31.7, 29.7, 29.6, 26.2, 25.9, 25.3, 18.1, K5.6; IR
2928–2855, 1632, 1642, 1111; HRMS: no identifiable ions
were observed.
4.5.5. Benzoic acid, 4-(tert-butyldimethylsilyldioxy)-1-
tridecen-6-yl ester (15e). YieldZ57 mg, 55%. RfZ0.43
1
(5% EA/hex); H d 8.04 (broad dd, 2H, JZ5.4, 2.2 Hz),
7.56–7.53 (1H), 7.45–7.42 (2H), 5.8 (ddt, 1H, JZ17.3, 10.7,
6.9 Hz), 5.29–5.22 (1H), 5.08 (broad dd, JZ17.0, 1.9 Hz),
5.05 (broad dd, 1H, JZ10.1, 1.9 Hz), 4.10–4.04 (1H),
2.55–2.42 (2H), 1.97–1.81 (2H), 1.76–1.60 (2H), 1.40–1.24
(10H), 0.92 (s, 3.5H), 0.916 (s, 5.4H), 0.86 (t, 3H, JZ
6.9 Hz), 0.13 (s, 4.3H), 0.10 (s, 1.7H); 13C d 166.05/166.01,
134.3, 134.1, 132.74/132.66, 130.8, 130.6, 129.56/129.51,
128.3, 117.5, 117.3, 81.58/81.55, 72.7, 72.1, 37.4, 36.7,
36.67, 36.0, 34.8, 34.4, 31.7, 29.5, 29.2, 26.1, 26.13, 25.2,
25.1, 22.6, 18.1, 14.0, K5.7; IR 2924–2859, 1719, 1638,
1458, 1500; HRMS: no identifiable ions were observed.
4.5.10. Ethyl-4-tert-butyldimethylsilyldioxy-4-(2-meth-
oxyethoxy)-2-trimethylsilylbutyrate (18). 4-Hydro-
peroxy-4-(2-methoxyethoxy)-2-trimethylsilyl-butyric acid
ethyl ester was prepared by ozonolysis of 2-trimethylsilyl-
pent-4-enoic acid ethyl ester in 2.9 g, 58% yield: RfZ0.33
1
(20% EA/hex); H d 10.1 (s, 0.5H), 10.0 (s, 0.5H), 4.71
(broad q, 2H, JZ5.7 Hz), 4.08–3.99 (1H), 3.81–3.68 (2H),
3.60–3.44 (2H), 3.36 (s, 1.4H), 3.35 (s, 1.6H), 2.23–2.15
(m, 0.5H), 2.09–1.96 (0.5H), 1.80 (broad dd, 1H, JZ
7.88 Hz),1.65 (broad dd, 1H, JZ6.3 Hz), 1.17 (broad dd,
3H, JZ6.9, 7.2 Hz), 0.16 (s, 5H), 0.01 (s, 4H); 13C d 175.7,
175.0, 106.9, 106.3, 72.5, 72.2, 66.1, 65.8, 60.0, 59.7, 58.8,
58.7, 33.2, 32.5, 28.1, 27.9, 14.2, K2.9, K3.0; IR 3335,
1716, 1252, 1100–1130; HRMS: no identifiable ions were
observed.
4.5.6. 2,2-Dimethylpropionic acid, 4-(tert-butyldimethyl-
silyldioxy)-1-tridecen-6-yl ester (15f). YieldZ35 mg,
1
55%. RfZ0.69 (5% EA/hex); H d 5.76 (ddt, 1H, JZ17.0,
10.4, 7.0 Hz), 5.07 (dd, 1H, JZ11.3, 1.6 Hz), 5.05 (dd, 1H,
JZ6.6, 1.9 Hz), 4.99–4.93 (m, 1H), 4.91–4.86 (0.2H), 3.99–
3.93 (0.8H), 2.51–2.26 (m, 2H), 1.82–1.65 (2H), 1.59–1.50
(2H), 1.31–1.22 (10H), 1.19 (s, 2.3H), 1.18 (s, 6.7H), 0.93
(s, 2.3H), 0.926 (s, JZ6.7 Hz), 0.87 (t, 3H, JZ6.9 Hz), 0.15
(s, 4.5H), 0.14 (s, 1.5H); 13C d 177.9, 177.8, 134.4, 134.2,
117.3, 117.2, 81.6, 81.58, 72.8, 71.6, 70.9, 45.2, 38.8, 38.7,
37.5, 36.8, 36.6, 36.1, 34.7, 34.3, 33.6, 31.7, 30.8, 29.43,
29.38, 29.2, 27.2, 26.2, 25.2, 25.1, 24.9, 22.6, 18.1, 14.0,
K5.67, K5.68; IR 2928–2855, 1734, 1642, 1286; HRMS:
no identifiable ions were observed.
Silylation of the hydroperoxide under standard conditions
afforded silyl peroxide 18 in 916 mg, 88% yield: RfZ0.67
(20% EA/hex); 1H d 4.86 (dd, 0.8H, JZ3.8, 7.9 Hz), 4.82–
4.80 (dd, 0.2H, JZ3.8, 7.9 Hz), 4.11–4.04 (1.4H), 4.03–
3.98 (0.6H), 3.76–3.71 (1.3H), 3.53–3.46 (2.7H), 3.34 (s,
0.6H), 3.33 (s, 2.4H), 2.22 (t, 0.7H, JZ2.2 Hz), 2.20 (0.3H),
2.14–1.56 (2H), 1.21 (broad t, 3H, JZ6.9 Hz), 0.90 (s, 6H),
0.83 (s, 3H), 0.14 (s, 2H), 0.04 (s, 4H), K0.01 (s, 9H); 13C d
174.7, 174.6, 107.7, 107.2, 72.0, 71.9, 69.7, 68.9, 59.7, 58.8,
58.7, 32.7, 32.6, 30.2, 28.9, 26.1, 25.63, 25.6, 18.06, 18.0,
14.4, 14.3, K2.76, K2.8, K3.0, K5.8. IR 2952–2859,
1714, 1464, 1252, 1160, 1100; HRFAB calcd for C18H40-
O6Si2Li (MCLi)C: 415.2523, found: 415.2527 (0.8 ppm).
4.5.7. Acetic acid, 3-(tert-butyldimethylsilyldioxy)-1-phe-
nyl-hex-5-enyl ester (15h). YieldZ11 mg, 10%. RfZ0.33
(5% EA/hex); 1H d 7.40–7.30 (5H), 5.90 (ddt, 1H, JZ17.3,
10.7, 6.9 Hz), 5.20 (broad dd, 1H, JZ17.0, 1.9 Hz), 5.12
(broad dd, 1H, JZ9.1, 1.9 Hz), 5.19–5.09 (1H), 4.05–3.90
(t, 0.5H, JZ6.6 Hz), 3.91 (t, 0.5H, JZ6.0 Hz), 2.05 (s,
1.5H), 2.04 (s, 1.5H), 1.64–1.56 (2H), 1.38–1.25 (2H), 0.944
(s, 4.6H), 0.936 (s, 4.4H), 0.152–0.148 (s, 6H); 13C d 171.1,
169.9, 141.1, 134.7, 134.2, 128.6, 128.5, 128.2, 127.8,
127.0, 126.5, 117.9, 117.4, 116.9, 84.6, 82.2, 81.0, 80.4,
73.2, 72.7, 64.5, 47.7, 39.3, 37.5, 37.3, 36.9, 31.7, 28.6,
26.2, 25.1, 21.1, 20.9, 18.2, K1.09, K5.6, K5.7; IR 2957–
2859, 1741, 1638, 1496, 1475, 1238; HRMS: no identifiable
ions were observed.
4.5.11. 4-tert-Butyldimethylsilyldioxy-2-trimethylsilyl-6-
heptenoic acid ethyl ester (19). The title compound was
prepared by allylation of 18 under standard conditions:
YieldZ200 mg, 55%. RfZ0.48 (5% EA/hex); 1H d 5.8 (ddt,
1H, JZ17.6, 10.4, 7.2 Hz), 5.08 (broad dd, 1H, JZ17.3,
1.6 Hz), 5.04 (broad dd, 1H, JZ10.1, 1.6 Hz), 4.14–4.04
(m, 2.3H), 3.93–3.83 (m, 0.7H), 2.55–1.96 (2H), 1.77–1.66
(0.5H), 1.70–1.66 (0.5H), 1.60–1.56 (2H), 1.21 (t, 2H, JZ
2.0 Hz), 1.99 (t, 1H, JZ2.0 Hz), 0.92 (s, 2.8H), 0.91 (s,
6.2H), 0.16 (s, 0.7H), 0.14 (s, 1.2H), 0.13 (s, 2H), 0.11 (s,
2.1H), 0.06 (s, 3.4H), 0.05 (s, 5.6H); 13C d 175.07/175.04,
134.6, 134.4, 117.0, 116.8, 101.6, 84.6, 84.2, 59.7, 59.6,
37.5, 35.7, 33.8, 33.1, 31.6, 29.4, 28.3, 26.2, 25.8, 22.6,
18.2, 18.1, 14.4, 14.0, K2.6, K2.68, K2.75, K5.7; IR
2949–2855, 1714, 1638, 1252; HRMS: no identifiable ions
were observed.
4.5.8. 3-But-3-enyloxy-1-(2-methoxyethoxy)-1-(tert-
butyldimethylsilyldioxy)-decane (16). YieldZ63 mg,
1
45%. RfZ0.34 (10% EA/hex); H d 5.81 (ddt, 1H, JZ
17.0, 10.1, 0.9 Hz), 5.07 (broad dd, 1H, JZ17.3, 1.6 Hz),
5.01 (broad dd, 1H, JZ10.1, 0.9 Hz), 4.86 (t, 0.5H, JZ
6.0 Hz), 4.07–4.03 (m, 0.5H), 3.80–3.76 (m, 1H), 3.58–3.50
(m, 2H), 3.40 (t, 2H, JZ6.9 Hz), 3.39 (2H, t, JZ6.6 Hz),
3.36 (s, 3H), 2.31 (broad q, 2H, JZ6.6 Hz), 1.66–1.53 (6H),
1.44–1.31 (8H), 0.93 (s, 9H), 0.88 (t, 3H, JZ6.3 Hz), 0.16
(s, 3.1H), 0.15 (s, 2.8H); 13C d 135.4, 116.1, 108.5, 72.3,
70.8, 70.2, 69.2, 58.9, 34.2, 32.3, 29.6, 26.1, 26.0, 24.6,
18.1, K5.7; IR 2923–2855, 1632, 1642, 1106; HRMS: no
identifiable ions were observed.
4.5.12. Formation of silatrioxepane: 3,3-di-tert-butyl-5-
heptyl-7-(2-methoxyethoxy)-3-sila-[1,2,4]-trioxepane
(20). 1-Hydroperoxy-1-(2-methoxyethoxy)-decan-3-ol
was prepared by ozonolysis of undecen-4-ol in

4668
A. Ahmed, P. H. Dussault / Tetrahedron 61 (2005) 4657–4670
2-methoxyethanol in 530 mg, 65% yield: RfZ0.37 (40%
EA/hex); 1H d 10.8 (s, 0.1H), 10.46 (s, 0.9H), 5.09 (t, 0.1H,
JZ4.7 Hz), 5.05–4.99 (0.9H), 3.91–3.85 (0.6H), 3.84–3.76
(2H), 3.64–3.52 (2H), 3.40 (s, 1.3H), 3.40 (s, JZ1.7 Hz),
3.36–3.34 (0.4H), 2.84 (broad peak, 2H), 1.91–1.23 (13H),
0.84 (broad t, 3H, JZ6.3 Hz); 13C d 106.2, 106.1, 72.6,
72.5, 68.4, 68.3, 66.9, 66.3, 66.5, 58.8, 38.7, 38.5, 37.4,
31.7, 31.0, 29.5, 29.1, 25.5, 25.4, 25.3, 22.5, 13.9; IR 3364,
1198, 1143, 1095; HRMS: no identifiable ions were
observed.
3H, JZ6.6 Hz); 13C d 134.4, 118.2, 72.9, 71.9, 42.64/42.60,
38.2, 31.8, 29.6, 29.2, 25.4, 22.6, 14.0.
Major diastereomer. RfZ0.49 (40% EA/hex); 1H d 5.8 (ddt,
1H, JZ16.4, 9.1, 5.4 Hz), 5.15–5.11 (2H), 4.01–3.96 (m,
1H), 3.93–3.90 (m, 1H), 2.44 (broad s, 2.0H), 2.28–2.25 (m,
2H), 1.62–1.60 (2H), 1.53–1.28 (12H), 0.88 (t, 3H, JZ
6.9 Hz); 13C d 134.7, 118.0, 69.3, 68.27, 42.1, 37.5, 31.8,
29.6, 29.2, 25.7, 22.6, 14.6, 14.0; IR 3347 (b), 1637;
HRFAB calcd for C13H26O2Li (MCLi)C: 221.2093, found:
221.2086 (3.2 ppm).
A solution of tert-BuSi(OTf)2 (700 mg, 0.6 mL, 1.6 mmol,
3.0 equiv) and imidazole (180 mg, 2.6 mmol, 5 equiv) in
DMF (2 mL) was stirred for few minutes, after which was
added a dropwise solution of the hydroperoxyalcohol
(140 mg, 0.53 mmol) in DMF (2 mL). After 15 min the
reaction mixture was quenched with DI water and extracted
into recycled 50% EA/hex (3!50 mL). The combined
organic layers were dried over Na2SO4 and concentrated.
Flash chromatography (20% EA/Hex) furnished 85 mg
(45%) of silatrioxepane (20): RfZ0.68 (20% EA/hex); 1H d
5.02 (t, 0.4H, JZ4.1 Hz), 4.93–4.91 (m, 0.6H), 4.10–4.12
(0.4H), 4.00–3.96 (0.6H), 3.71–3.59 (2H), 3.56–3.51 (2H),
3.375 (s, 1.1H), 3.372 (s, 1.9H), 2.23–2.18 (0.8H), 1.92–
1.83 (m, 1.2H), 1.57–1.26 (12H), 1.07 (s, 5.7H), 1.05 (s,
3.3H), 1.03 (s, 2.8H), 1.0 (s, 6.2H), 0.87 (broad t, 3H, JZ
6.0 Hz); 13C d 107.4, 104.4, 71.9, 71.5, 70.6, 67.2, 67.1,
59.0, 58.98, 40.6, 40.4, 38.6, 37.5, 31.8, 31.7, 29.5, 29.44,
29.37, 29.3, 29.1, 28.1, 28.0, 27.9, 27.7, 27.5, 27.2, 27.0,
26.9, 26.7, 25.9, 25.3, 24.9, 22.6, 21.9, 21.5, 20.5, 20.3,
14.1; IR 2933–2850, 1111; HRFAB calcd for C21H44O5-
SiNa (MCNa)C: 427.2858, found: 427.2867 (2.7 ppm).
4.5.15. Formation of acetonides: 4-(2-propenyl)-6-hep-
tyl-2,2-dimethyl-1,3-dioxane (23). Into a solution of diol
22 (100 mg, 0.46 mmol) in 2,2-dimethoxypropane (6 mL,
excess), was added a catalytic amount of S-(C)-camphor
sulphonic acid (5 mg). The reaction mixture was stirred for
twenty minutes, after which solvent was removed in vacuo.
The crude product was purified by flash chromatography
(5% EA/hex) to furnish 71 mg (60%) of a mixture of
1
diastereomeric acetonides: RfZ0.65 (10% EA/hex); H d
5.88 (ddt, 1H, JZ17.3, 10.0, 6.9 Hz), 5.09 (broad dd, 1H,
JZ17.3, 1.9 Hz), 5.04 (broad dd, 1H, JZ10.4, 1.8 Hz),
3.88–3.81 (m, 1H), 3.79–3.72 (m, 1H), 2.32–2.26 (1H),
2.20–2.11 (1H), 1.51–1.47 (4H), 1.38 (s, 3H), 1.339 (s, 3H),
1.30–1.27 (10H), 0.87 (t, 3H, JZ6.9 Hz).
Mixture of diastereomers. DEPT 135 13C d 134.6 (C),
134.3 (C), 116.9 (K), 116.7 (K), 100.1 (K), 98.3 (K),
69.0 (C), 68.7 (C), 66.6 (C), 66.2 (C), 40.9 (K), 40.2
(K), 38.2 (K), 36.5 (K), 36.49 (K), 36.0 (K), 31.8 (K),
30.3 (C), 29.7 (K), 29.55 (K), 29.5 (K), 29.23 (K), 29.21
(K), 25.3 (K), 24.95 (C), 24.87, 24.8 (C), 22.6 (K), 19.8
(C), 14.0 (C); IR 1638, 1165, 1116; HREI calcd for
C15H27O2 (MKCH3)C: 239.2011; found: 239.2012
(0.4 ppm).
4.5.13. 3,3-Di-tert-butyl-5-heptyl-7-(2-propenyl)-1,2,4,3-
trioxasilepane (21). The title compound was prepared by
allylation of 20 under conditions similar to those described
for compound 15d: yieldZ4 mg, 5%. RfZ0.78 (5% EA/
4.5.16. Tridecane-4, 6-diol (24). Peroxide 15c (345 mg,
0.8 mmol), and BHT (5 mg), were dissolved in THF/AcOH/
H2O (5:3:2, 10 mL). Following disappearance of starting
material (2 days, TLC), triphenyl phosphine (4 mmol, 1 g)
was added. After an additional 24 h, the reaction mixture
was diluted with 50 mL of 40% recycled EA/hex, and
washed sequentially with saturated NH4Cl (4!20 mL)
solution and brine solution (2!15 mL). The separated
organic layers were dried over Na2SO4 and concentrated in
vacuo. Flash chromatography (5% EA/hex) furnished
217 mg (89%) of 4-hydroxy 6-benzyloxy tridecene as an
inseparable mixture of diastereomers. RfZ0.2 (5% EA/
1
hex); H d 5.86 (ddt, 1H, JZ17.3, 10.1, 6.9 Hz), 5.07 (dd,
1H, JZ17.3, 1.6 Hz), 5.05 (dd, 1H, JZ9.1, 1.3 Hz), 4.16
(m, 1H), 4.08 (m, 1H), 2.43–2.37 (1H), 2.24–2.18 (m, 1H),
1.78–1.67 (2H), 1.63–1.56 (1H), 1.43–1.28 (11H), 1.0 (s,
4.6H), 0.99 (s, 4.4H), 0.96 (s, 4.6H), 0.95 (s, 4.4H), 0.88
(broad t, 3.0H, JZ6.9 Hz); 13C d 135.3, 116.7, 100.8, 70.0,
42.3, 38.2, 37.9, 31.8, 29.7, 29.5, 29.3, 27.6, 27.5, 27.3,
27.1, 25.6, 22.6, 21.0, 14.1, 9.4, 2.1; IR 2930–2848, 1638,
1247, 1073; HRMS: no identifiable ions were observed.
4.5.14. Reduction of peroxides: tridec-1-ene-4,6-diol
(22). Into a solution of allylated peroxide 15d (201 mg,
0.52 mmol) in THF (6 mL) was added LiAlH4 (2.6 mmol,
99 mg). The reaction was stirred overnight, and then
quenched with dilute HCl. The extracts (50% recycled
EA/hex, 3!15 mL) were dried over Na2SO4, and solvent
was removed in vacuo. The crude product was purified by
flash chromatography (20% EA/hex) to furnish 62 mg
(55%) and 35 mg (35%) of diastereomeric diols.
1
hex); H d 7.35–7.27 (5H), 5.84 (ddt, 1H, JZ17.3, 10.4,
7.2 Hz), 5.14 (dd, 1H, JZ17.0, 1.9 Hz), 5.12 (dd, 1H, JZ
10.0, 2.0 Hz), 4.64 (d, 0.6H, JZ11.3 Hz), 4.44 (d, 0.6H, JZ
11.3 Hz), 4.56 (dd, 0.5H, JZ11.3, 15.3 Hz), 3.99–3.94
(0.3H), 3.86–3.81 (1H), 3.73–3.65 (1H), 3.53 (s, 0.9H), 2.78
(s, 0.1H), 2.27–2.17 (2H), 1.72–1.50 (4H), 1.37–1.24
(broad, 10H), 0.90 (t, 3H, JZ6.9 Hz); 13C d 138.2, 135.0,
134.9, 128.4, 128.3, 127.8, 127.7, 127.6, 117.3, 117.1, 79.6,
71.2, 70.7, 70.6, 67.8, 42.2, 42.1, 40.5, 39.7, 33.6, 33.5,
31.7, 29.8, 29.7, 29.2, 25.4, 24.7, 22.6, 13.9; IR 3449, 1647,
1494, 1451; HREI calcd for C20H33O2 (MCH)C: 305.2481;
found: 305.2483 (0.9 ppm).
1
Minor diastereomer. RfZ0.51 (40% EA/hex); H d 5.81
(ddt, 1H, JZ16.4, 9.5, 6.9 Hz), 5.08 (dd, 1H, JZ17.0,
1.9 Hz), 5.04 (dd, 1H, JZ10.4, 2.2 Hz), 3.93–3.88 (m, 1H),
3.87–3.82 (m, 1H), 2.88 (broad s, 2H), 2.29–2.19 (m, 2H),
1.64–1.60 (2H), 1.52–1.39 (4H), 1.33–1.24 (8H), 0.88 (t,
A mixture of 4-hydroxy-6-benzyloxy tridecene (217 mg,

A. Ahmed, P. H. Dussault / Tetrahedron 61 (2005) 4657–4670
4669
0.71 mmol) and 10% Pd/C (10 mol%, 76 mg) in MeOH
(5 mL) was placed under an atmosphere of H2 (balloon).
After 3 days, the reaction mixture was filtered through a
plug of cotton and the solvent was removed under reduced
pressure. Flash chromatography (20% EA/Hex) furnished
tridecane-4,6-diol (24) as a mixture of two diastereomers in
a total yield of 78%. The first eluting diastereomer was a
colorless oil (86 mg). The second eluting isomer was a
white solid (35 mg).
4.56–4.54 (m, 0.8H), 4.47–4.43 (0.2H), 4.01–3.98 (m,
0.2H), 3.49–3.46 (0.8H), 2.44–2.30 (2H), 1.75–1.59 (2H),
1.36–1.29 (8H), 1.25 (s, 7.5H), 1.23 (s, 1.5H), 0.89 (t, 3H,
JZ6.9 Hz); 13C d 134.7, 134.3, 117.3, 117.2, 85.7, 85.0,
80.5, 80.4, 40.8, 38.6, 36.4, 36.0, 34.4, 34.2, 31.6, 30.3,
29.9, 29.7, 28.53, 28.49, 26.7, 26.5, 22.6, 22.2, 14.1; IR
1642, 1243, 1199; HRMS: no identifiable ions were
observed.
Allylation of peroxyacetals 5 and 14a,b was carried out
under similar procedures as described earlier.
Major diastereomer. RfZ0.3 (20% EA/hex); 1H d 3.81–3.80
(2H), 3.53 (broad peak, 2H), 1.58–1.26 (18H), 0.9 (t, 3H,
JZ6.3 Hz), 0.85 (t, 3H, JZ6.3 Hz); 13C d 73.1, 72.8, 42.7,
40.32, 38.2, 31.8, 29.6, 29.2, 25.3, 22.6, 18.5, 14.0, 13.99;
IR 3294, 1062.
4.5.20. 1-Triphenylsilyl-4-penten-2-yl tert-butyldi-
methylsilylperoxide (28). The title compound was prepared
by allylation of triphenylsilyl peroxyacetal 5. YieldZ
118 mg, 60%. RfZ0.33 (2% EA/hex); 1H d 7.75–7.64
(6H), 7.48–7.40 (9H), 5.80 (ddt, 1H, JZ17.0, 10.1, 6.9 Hz),
5.05 (dd, 1H, JZ10.7, 1.9 Hz), 4.88 (1H, dd, JZ17.0,
1.6 Hz), 4.35 (m, 1H), 2.24 (m, 2H), 0.96 (d, 2H, JZ
7.8 Hz), 0.98 (s, 9H), 0.18–0.10 (overlapping s, 6H). 13C d
135.7, 134.9, 134.5, 129.5, 127.8, 117.2, 82.2, 38.9, 26.1,
18.1, 16.9, 2.0, K5.5, K5.6; IR 1639, 1493, 1477, 1362;
HRFAB calcd for C29H38O2Si2Li (MCLi)C: 481.2571;
found: 481.2583 (2.4 ppm).
1
Minor diastereomer. Mp 55–56 8C; H d 3.93–3.89 (2H),
2.53 (broad peak, 2H), 1.60–1.28 (18H), 0.92 (t, 3H, JZ
6.3 Hz), 0.87 (t, 3H, JZ6.3 Hz); 13C d 69.4, 69.1, 42.3, 39.6,
37.5, 31.8, 29.6, 29.2, 25.8, 22.6, 18.9, 14.0, 12.1; HRFAB
calcd for C13H28O2Li (MCLi)C: 223.2249, found:
223.2240 (4.1 ppm).
4.5.17. 2,2-Dimethyl- 4-heptyl-6-propyl-1,3-dioxane (25).
Into a solution of diol 24 (70 mg, 0.32 mmol) in 2,2
dimethoxypropane (4 mL, excess), was added (S)-(C)-
camphor sulfonic acid (5 mg). After 30 min solvent was
removed in vacuo. Flash chromatography (5% EA/hex)
furnished 80 mg (96%) of acetonide. RfZ0.5 (5% EA/hex)
1H d 3.80–3.73 (2H), 1.54–1.44 (3H), 1.40 (s, 3H), 1.36 (s,
3H), 1.34–1.25 (14H), 1.07 (q, 1H, JZ11.9 Hz), 0.88 (t, 3H,
JZ6.6 Hz), 0.86 (t, 3H, JZ6.6 Hz); DEPT 135 13C d 69.0
(C), 68.7 (C), 38.6 (K), 37.0 (K), 36.5 (K), 31.8 (K),
30.3 (K), 29.5 (K), 29.2 (K), 24.9 (K), 22.6 (K), 19.8
(C), 18.1 (K), 14.0 (C), 13.97 (C), 12.1 (K); IR 1165,
1116; HREI calcd for C13H28O2Li (MCH)C: 257.2481,
found: 257.2483 (0.9 ppm).
4.5.21. 7-Methoxy-tridec-1-en-4-yl tert-butyldimethyl-
silyl peroxide (29a). The title compound was prepared by
allylation of peroxyacetal 14a. YieldZ87 mg, 78%. RfZ
1
0.73 (10% EA/hex); H d 5.80 (ddt, 1H, JZ17.0, 10.1,
6.9 Hz), 5.06 (dd, 1H, JZ17.0, 1.6 Hz), 5.04 (dd, 1H, JZ
9.1, 1.9 Hz), 3.91 (m, 1H), 3.30 (s, 3H), 3.11 (m, 1H), 2.49–
2.43 (1H), 2.31–2.20 (1H), 1.64–1.18 (14H), 0.93 (s, 9H),
0.88 (t, 3H, JZ6.3 Hz), 0.15 (s, 3.4H), 0.14 (s, 2.6H); 13C d
134.7, 116.8, 84.9, 84.7, 80.9, 80.7, 56.3, 56.2, 37.0, 33.45/
33.41, 31.8, 29.7, 29.5, 29.2, 28.8, 27.6, 26.2, 26.1, 25.3,
25.2, 22.6, 18.2, 14.0, K5.6; IR 2954–2810, 1650, 1193,
1093; HRMS: no identifiable ions were observed.
4.5.18. 4-tert-Butyldioxy-5-iodo-dodec-1-ene (26). Into a
K78 8C solution of iodoperoxy acetal (0.35 mmol, 134 mg)
3a and allylsilane (2 equiv, 0.7 mmol, 0.1 mL) in CH2Cl2
(5 mL) was added drop wise SnCl4 (1.1 equiv, 0.4 mL,
1.0 M in CH2Cl2). After 30 min the reaction mixture was
quenched with DI water and allowed to warm to room
temperature. The combined extracts (recycled 50% EA/hex,
3!30 mL) were dried over Na2SO4 and concentrated. Flash
chromatography (2% EA/Hex) furnished allylated peroxide
in 48 mg, 35% yield. RfZ0.88 (2% EA/hex); 1H d 5.89 (ddt,
1H, JZ17.0, 10.0, 6.9 Hz), 5.14 (dd, 1H, JZ17.3, 1.6 Hz),
5.08 (dd, 1H, JZ10.1, 1.8 Hz), 4.51 (dt, 1H, JZ9.8,
4.1 Hz), 4.41 (m, 0.1H), 3.95 (m, 0.1H), 3.46 (m, 0.9H),
2.40–2.37 (2H), 1.86–1.58 (3H), 1.40–1.26 (broad 9H), 1.25
(s, 8.2H), 1.23 (s, 1.1H), 0.88 (t, 3H, JZ6.6 Hz); 13C d
134.7/134.3, 117.3/117.2, 85.0, 80.4, 40.4, 36.5, 36.0, 31.8,
29.9, 29.8, 29.11/29.07, 28.8, 26.7, 26.5, 22.6; IR 2977–
2844, 1643, 1358, 1252, 1196; HRFAB calcd for C13H26IO2
(MKallyl)C: 341.0978; found: 341.0207 (22 ppm).
4.5.22. 4-tert-Butyldimethyl silyldioxy-7-iodo-tridec-1-
ene (29b). The title compound was prepared by allylation
of acetal 14b under standard conditions. YieldZ68 mg,
1
30%. RfZ0.8 (2% EA/hex); H d 5.80 (ddt, 1H, JZ17.0,
10.1, 6.9 Hz), 5.08 (broad dd, 1H, JZ17.0, 1.6 Hz), 5.06
(broad dd, 1H, JZ10.1, 1.6 Hz), 4.15–4.07 (1H), 3.95–3.89
(1H), 2.49–2.42 (1H), 2.31–2.23 (1H), 1.95–1.63 (5H),
1.47–1.24 (9H), 0.94 (s, 9H), 0.90 (t, 3H, JZ6.6 Hz), 0.16
(s, 2.4H), 0.15 (s, 3.6H); 13C d 134.43/134.40, 84.2, 83.7,
40.71, 40.68, 39.8, 39.76, 36.9, 36.7, 36.2, 32.0, 31.8, 31.7,
29.7, 29.5, 29.4, 28.5, 26.2, 22.6, 18.2, 14.0, K5.62, K5.64;
IR 1642, 1247, 1151; HRMS: no identifiable ions were
observed.
Acknowledgements
4.5.19. 4-tert-Butyldioxy-5-iodo-undec-1-ene (27). The
title compound was prepared by allylation of iodoperoxy
acetal 4a at 0 8C (43 mg, 23%). RfZ0.63 (2% EA/hex); 1H d
5.90 (ddt, 1H, JZ17.3, 10.4, 7.2 Hz), 5.15 (broad dd, 1H,
JZ17.0, 1.6 Hz), 5.08 (broad dd, 1H, JZ10.1, 1.6 Hz),
We thank the NIH for financial support and Dr. Dipanjan
Nag for assistance with NMR experiments. NMR spectra
were recorded on equipment purchased with NSF support
(MRI 0079750 and CHE 0091975).

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A. Ahmed, P. H. Dussault / Tetrahedron 61 (2005) 4657–4670
Valentine, J. S., Greenberg, A., Liebman, J. F., Eds.; Blackie A
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