Synthesis of cyclic N-tosyliminocarbonates by Lewis acid catalyzed allylic substitution of trichloroacetimidates

Article abstract of DOI:10.1002/ejoc.201200378

Allylic trichloroacetimidates bearing a δ-N-tosylcarbamoyloxy group were prepared in two steps from the corresponding diols, and their Bronsted and Lewis acid catalyzed cyclization reactions were investigated. It was found that N-tosylcarbamates derived from secondary and tertiary alcohols bearing alkyl substituents undergo a chemoselective allylic alkylation to give N-tosyliminocarbonates in good isolated yields. In turn, aryl-substituted substrates tend to give oxazolines by abstraction of the carbamate functionality. The cyclization of N-tosylcarbamates derived from secondary alcohols preferentially give trans-iminocarbonates. However, the trans selectivity varied and depended on the substitution pattern, configuration of the substrate, and the catalyst. A high trans selectivity could be achieved from (E) substrates by using TMSOTf as the catalyst. The synthetic utility of iminocarbonates was demonstrated by transforming them into 1,2-diols and cyclic carbonates as well as into N-tosyloxazolidinones by a halide ion-induced rearrangement. Copyright

Full text of DOI:10.1002/ejoc.201200378

Job/Unit: O20378
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DOI: 10.1002/ejoc.201200378
Synthesis of Cyclic N-Tosyliminocarbonates by Lewis Acid Catalyzed Allylic
Substitution of Trichloroacetimidates
Liene Grigorjeva[a] and Aigars Jirgensons*[a]
Keywords: Synthetic methods / Nitrogen heterocycles / Nucleophilic substitution / Cyclization / Lewis acids / Allylic
compounds
Allylic trichloroacetimidates bearing a δ-N-tosylcarbamoyl-
clization of N-tosylcarbamates derived from secondary
oxy group were prepared in two steps from the correspond- alcohols preferentially give trans-iminocarbonates. However,
ing diols, and their Brønsted and Lewis acid catalyzed cycli-
zation reactions were investigated. It was found that N-tosyl-
carbamates derived from secondary and tertiary alcohols
bearing alkyl substituents undergo a chemoselective allylic
alkylation to give N-tosyliminocarbonates in good isolated
yields. In turn, aryl-substituted substrates tend to give oxaz-
olines by abstraction of the carbamate functionality. The cy-
the trans selectivity varied and depended on the substitution
pattern, configuration of the substrate, and the catalyst. A
high trans selectivity could be achieved from (E) substrates
by using TMSOTf as the catalyst. The synthetic utility of
iminocarbonates was demonstrated by transforming them
into 1,2-diols and cyclic carbonates as well as into N-tosyl-
oxazolidinones by a halide ion-induced rearrangement.
iminocarbonates through a silver(I)-promoted substitution
of allyl diiodides which, in turn, were prepared by the
iodination of allenyl N-tosylcarbamates. On the basis of
their results, it was expected that the intramolecular acid-
catalyzed allylic substitution of the imidate group in N-
tosylcarbamates 1 (see Figure 1) should give N-tosylimino-
carbonates 2 as the major products. This would comple-
ment an application of N-tosylcarbamates as O-nucleo-
philes in palladium(II)- and palladium(0)-catalyzed allylic
substitutions that lead to oxazolidinones 3.[7] In principle,
the cyclization of substrate 1 could also result in the forma-
tion of oxazoline 4, by elimination of the carbamate group.
Introduction
Allylic substitutions to form C–heteroatom bonds have
been achieved with a range of nucleophiles by using late
transition-metal catalysts.[1] However, over the last decade,
Lewis or Brønsted acid catalysts have emerged as a more
eco-friendly and cheaper alternative. Allylic alcohols,[2]
carboxylates,[2c,3] halides,[4] and trichloroacetimidates[5]
have been used as substrates to achieve acid-catalyzed intra-
molecular substitution with N- and O-nucleophiles.
Our recent work was devoted to the cyclization of allylic
bis(trichloroacetimidates) leading to 4-vinyloxazolines,
highly versatile amino alcohol and amino acid precur-
sors.[5f,5g] It was rationalized that the cyclization of bis-
(trichloroacetimidates) involves the substitution of a Lewis
or Brønsted acid complexed imidate group with another im-
idate as the N-nucleophile. With these results, we began
work to extend the scope of the acid-catalyzed allylic tri-
chloroacetimidate substitution with other nucleophiles.
Iminocarbonates are valuable intermediates for the syn-
theses of 1,2-diols and 1,2-amino alcohols.[4,6] Nevertheless,
there are a limited number of reports for the syntheses of
iminocarbonates, and most of them involve the reaction of
1,2-diols with isocyanates.[6] An alternative method was re-
ported by Giroux and Friesen.[4] They prepared N-tosyl-
[a] Latvian Institute of Organic Synthesis,
Aizkraukles 21, 1006 Riga, Latvia
Fax: +371-675-414-08
E-mail: aigars@osi.lv
Homepage: http://osmg.osi.lv
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201200378.
Figure 1. Potential products 2–4 in the cyclization of allylic tri-
chloroacetimidates 1 bearing δ-N-tosylcarbamoyloxy group.
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L. Grigorjeva, A. Jirgensons
FULL PAPER
However, we hypothesized that the complexation of the acid Table 1. Substitution pattern and yields of monoimidates 6 and N-
tosylcarbamates 1.
catalyst to the more basic imidate group would provide
iminocarbonate 2, selectively.
Entry
R1
R2
% Yield[a]
6
% Yield[a]
1
Herein we report the syntheses of N-tosyliminocarbon-
ates 2 through an acid-catalyzed intramolecular substitu-
tion of the allylic trichloroacetimidate moiety in N-tosyl-
carbamates 1.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
n-pentyl
n-pentyl
iPr
iPr
H
H
H
H
H
H
H
H
H
H
Me
(E)-6a, 78
(Z)-6a, 76
(E)-6b, 84
(Z)-6b, 87
(E)-6c, 80
(E)-6d, 83
(E)-6e, 82
(E)-6f, 68
(Z)-6f, 72
(E)-6g, 80
(E)-6h, 84
(E)-6i, 91
(E)-6j, 91
(E)-6k, 71
(E)-1a, 94
(Z)-1a, 97
(E)-1b, 96
(Z)-1b, 96
(E)-1c, 90
(E)-1d, 97
(E)-1e, 96
(E)-1f, 85
(Z)-1f, 95
Bn
CH2=CH(CH2)8–
Ph2CH–
Ph
Ph
p-MeOPh
Me
–CH2(CH2)3CH2–
–(CH2)2NBoc(CH2)2–
–(CH2)2O(CH2)2–
Results and Discussion
Substrates 1 were synthesized according to the general
strategy shown in Scheme 1. Diols (E)-5a–(E)-5k, (Z)-5a,
(Z)-5b, and (Z)-5f (see Scheme 1) were prepared in two
steps by the addition of propargyl alcohol to the respective
aldehyde or ketone followed by a stereoselective reduction
of the triple bond (see Supporting Information).[5f] Next,
the treatment of 5 with 1 equiv. of trichloroacetonitrile in
the presence of 20 mol-% DBU (1,8-diazabicyclo[5.4.0]un-
dec-7-ene) afforded monoimidates 6 in good to excellent
yields (see Table 1). Finally, the reaction of imidates 6 with
tosylisocyanate provided the products (E)-1a–(E)-1f, (E)-
1h–(E)-1k, (Z)-1a, (Z)-1b, and (Z)-1f in almost quantitative
yields (see Scheme 1, Table 1). The only exception was imid-
ate 6g which did not afford the expected carbamate 1g, but
instead formed oxazoline 4g when treated with tosyl iso-
cyanate (Table 1, Entry 10).
[b]
–
(E)-1h, 93
(E)-1i, 96
(E)-1j, 97
(E)-1k, 87
[a] Isolated yield. [b] Vinyloxazoline 4g was isolated in 85% yield.
strate (E)-1a was subjected to 1 equiv. of AlCl3. This re-
sulted in complete conversion of the starting material in
2 h, but provided a product mixture that was difficult to
separate. 1H NMR and GC–MS analyses suggested that the
major product formed was a derivative of (E)-1 in which
both the imidate and carbamate groups were substituted by
chlorine. Likely, substitution reactions with the nucleophilic
counterions competed with the cyclization leading to the
deactivation of the Lewis acid catalysts.
Other substrates were subsequently subjected to the
BF3·OEt2, B(C6F5)3, TMSOTf, Cu(OTf)2, and Cu2(OTf)2·
C6H6 catalysts. N-Tosylcarbamates (E)-1a–(E)-1e, (E)-1h–
(E)-1k, (Z)-1a, and (Z)-1b gave the corresponding imino-
carbonates 2a–2e and 2h–2k as the intramolecular substitu-
tion products in good to excellent yields, when exposed to
previously established Lewis acid catalysts (see Tables 2 and
3). A mixture of products (with oxazoline 4f as the major
component) was obtained from substrates (E)-1f and (Z)-
1f bearing a phenyl group (see Table 2, Entries 22 and 23).
This implies that the method is not applicable if a very
stable carbenium ion is generated by the abstraction of the
tosylcarbamate. Nevertheless, tosylcarbamates (E)-1h–(E)-
1k, derived from tertiary alcohols, were still suitable sub-
strates for the syntheses of iminocarbonates 2h–2k (see
Table 3).
Scheme 1. Preparation of δ-N-tosylcarbamates 1.
Substrate (E)-1a was used as a model compound for the
The proposed structure of compound 2i was corrobo-
1
initial screening of the catalysts. The treatment of (E)-1a rated by 2D H/13C HSQC (heteronuclear single quantum
with 10 mol-% of CuCl, NiCl2, MgCl2, Ti(OiPr)4, AlCl3, correlation) and HMBC (heteronuclear multiple bond cor-
Zn(OTf)2, B-butyl-9-BBN (9-butyl-9-borabicyclo[3.3.1]- relation) NMR experiments (see Supporting Information).
nonane), BEt3, Et2AlCl, CuI, CuCl2, Me3Al, PPTS (pyrid- The characteristic 13C NMR shift for the allylic carbon in
inium para-toluenesulfonate), HCl in Et2O, and BBr3 in a iminocarbonates 2 (δC ≈ 80 ppm) easily allowed us to distin-
CH2Cl2 solution did not lead to detectable conversion, by guish them from the regioisomeric oxazolidinones 3 (δC
≈
TLC, of the starting material. A slow conversion (ca. 50% 60 ppm). The trans configuration for iminocarbonates
in 3 d) was observed by using TFA (trifluoroacetic acid) as trans-2a–trans-2e was revealed by NOESY NMR experi-
a catalyst. Finally, 10 mol-% of BF3·OEt2, B(C6F5)3, ments (see Supporting Information). In addition to these
TMSOTf, Cu(OTf)2, and Cu2(OTf)2·C6H6, were found to spectroscopic studies, the structures of trans-2a–trans-2c
be efficient catalysts for the cyclization reaction of (E)-1a. and 2i–2k were confirmed by transforming them into
The efficiency of these catalysts could be attributed to the known compounds (vide infra). Finally, the structure of
sufficient Lewis acidity and lack of nucleophilic counteri- iminocarbonate 2i was unambiguously proved by single-
ons. To gain evidence for the effect of the counterion, sub- crystal X-ray diffraction (see Supporting Information).
2
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Synthesis of Cyclic N-Tosyliminocarbonates
Table 2. Cyclization of N-tosylcarbamates 1a–1f derived from secondary alcohols.
Entry
R1
Substrate
Lewis acid
Time [h]
% Yield[c]
trans/cis ratio[d]
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
n-pentyl
n-pentyl
n-pentyl
n-pentyl
n-pentyl
n-pentyl
n-pentyl
iPr
iPr
iPr
iPr
iPr
iPr
Bn
Bn
Bn
(E)-1a
(Z)-1a
(E)-1a
(Z)-1a
(E)-1a
(E)-1a
(E)-1a
(E)-1b
(Z)-1b
(E)-1b
(Z)-1b
(E)-1b
(E)-1b
(E)-1c
(E)-1c
(E)-1c
(E)-1c
(E)-1d
(E)-1d
(E)-1e
(E)-1e
(E)-1f
(Z)-1f
BF3·OEt2
BF3·OEt2
TMSOTf
TMSOTf
Cu(OTf)2
CuOTf[a]
B(C6F5)3
BF3·OEt2
BF3·OEt2
TMSOTf
TMSOTf
Cu(OTf)2
B(C6F5)3
BF3·OEt2
TMSOTf
Cu(OTf)2
B(C6F5)3
BF3·OEt2
TMSOTf
BF3·OEt2
TMSOTf
BF3·OEt2
BF3·OEt2
24
72[b]
4
2a, 72
2a, 87
2a, 82
2a, 51
2a, 76
2a, 75
2a, 73
2b, 90
2b, 85
2b, 80
2b, 70
2b, 80
2b, 75
2c, 73
2c, 70
2c, 74
2c, 63
2d, 69
2d, 75
2e, 85
2e, 82
4f, 44
n.d.[e]
15:1
5:1
34:1
4:1
6:1
2:1
72[b]
60[b]
80[b]
80[b]
18
3:1
15:1
80:1
14:1
50:1
25:1
35:1
3:1
25:1
6:1
5:1
48[b]
3
72[b]
20
26
48[b]
22
48[b]
48[b]
26[b]
26[b]
3
Bn
CH2=CH(CH2)8
CH2=CH(CH2)8
Ph2CH
6:1
11:1
14:1
45:1
–
Ph2CH
Ph
Ph
2.5
24
24
–
[a] Cu2(OTf)2·C6H6. [b] Additional portions of Lewis acid (10 mol-%) were added after each 24 h. [c] Isolated yield. [d] Determined by
1
using H NMR, LC–MS and HPLC (210 nm). Ratio is given as determined by HPLC. [e] n.d. = not determined.
Table 3. Cyclization of tosylcarbamates (E)-1h–(E)-1k derived from tertiary alcohols (E)-1h–(E)-1k. However, when using
tertiary alcohols.
BF3·Et2O as the catalyst, the yields were slightly better (see
Table 3).
As can be seen from Table 2, the N-tosylcarbamates de-
rived from secondary alcohols 1a–1e provided the trans-
iminocarbonates trans-2a–trans-2e, preferentially (see
Table 2). The trans selectivity varied depending on the con-
figuration of the double bond and the substitution pattern
in substrates (E)- and (Z)-1a–(E)- and (Z)-1b as well as on
the Lewis acid catalyst. Isomer (E)-1a, bearing the n-pentyl
Entry
R1, R2
Substrate Catalyst Time % Yield 2[a]
substituent, resulted in considerably better trans selectivity
in comparison to isomer (Z)-1a, when BF3·OEt2, TMSOTf,
and Cu(OTf)2 were used as catalysts (see Table 2, Entries 1–
4), from which TMSOTf was superior. The exposure of sub-
strates (E)- and (Z)-1b, bearing the sterically more de-
manding isopropyl substituent, to BF3·OEt2, TMSOTf, Cu-
(OTf)2, and B(C6F5) catalysts gave iminocarbonate 2b with
a high trans selectivity from both isomers (see Table 2, En-
tries 8–13). Although in this case, isomer (Z)-1b appeared
to give a higher trans selectivity.
In the literature, the origin of this diastereoselectivity has
been studied for several acid-catalyzed intramolecular all-
ylic substitutions with both O- and N-nucleophiles.[2c,2e]
These studies reveal that the given reactions are reversible
leading to a thermodynamically controlled diastereomeric
1
2
3
4
5
6
7
Me
Me
(E)-1h BF3·OEt2 18 h
2h, 93
2h, 77
2i, 90
(E)-1h
(E)-1i
(E)-1i
(E)-1j
(E)-1j
TMSOTf 0.5 h
BF3·OEt2 1 h
TMSOTf 10 min 2i, 74
BF3·OEt2 1 h 2j, 88
TMSOTf 10 min 2j, 80
2k, 83
–CH2(CH2)3CH2–
–CH2(CH2)3CH2–
–(CH2)2NBoc(CH2)2–
–(CH2)2NBoc(CH2)2–
–(CH2)2O(CH2)2–
(E)-1k BF3·OEt2 1 h
[a] Isolated yield.
Substrates with the (E)-configured double bond reacted
in shorter times (see Table 2, Entries 1 vs. 2, Entries 3 vs. 4,
Entries 8 vs. 9, and Entries 10 vs. 11), particularly if
TMSOTf was used as a catalyst (see Table 2, Entries 3, 10,
and 15). In addition, using TMSOTf induced a faster con-
version in the cases of the N-tosylcarbamates derived from
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ratio. We subjected the diastereomeric mixtures of 2a and tion of the substrate are prerequisites to induce the faster
2b, enriched with the minor isomer (2a, trans/cis, 3:1; 2b, and trans selective pathway through the SN2Ј mechanism.
trans/cis, 6:1), to 10 mol-% TMSOTf. No changes in the Alternatively, the SN1 mechanism through the intimate ion
isomeric ratios were observed for 2a over 4 h or for 2b over pair can be invoked, assuming that no change takes place
3 h, suggesting that the cyclization reactions of N-tosylcar- in the double-bond configuration of the intermediate car-
bamates 1 to N-tosyliminocarbonates 2 are kinetically con- benium ion, when starting from (E)-1 or (Z)-1. However, in
trolled.
the case of substrate (Z)-1a compared to (E)-1a, this could
The chemoselective cyclization of substrates 1 leading to not explain the less trans selective reaction.
iminocarbonates 2 could be explained by the complexation
To demonstrate the utility of the iminocarbonates, the
of the Lewis acid to the most basic imidate functionality,[8] cyclization products 2a, 2c, and 2i–2k were hydrolyzed un-
leading to an allylcarbenium ion which prefers to react with der basic reaction conditions to the corresponding diols 7a,
the harder oxygen versus nitrogen center of the N-tosyl- 7c, and 7i–7k (see Table 4). Thus, the cyclization of N-tosyl-
carbamate, analogous to the mechanism proposed by carbamates 1, derived from secondary alcohols, followed by
Friesen and Giroux (see Figure 2).[4] It is evident, however, hydrolysis represents a new method for syntheses of syn-
that for formation of iminocarbonates 2, the SN1-type 1,2-diols, as exemplified by the transformation of trans-
mechanism involving a solvent-separated ion pair is not the iminocarbonates, that is, trans-2a and trans-2c into the diols
(only) operational pathway. Such a mechanism would lead syn-7a and syn-7c.
to a constant trans/cis product ratio independent of the cat-
alyst and configuration of substrate 1. The varying trans/cis
ratio (see Table 2) could be explained by an SN2Ј reaction
Table 4. Hydrolysis of iminocarbonates 2 to diols 7.
mechanism (see Figure 2). The differences in the reaction
rates for (E)-1 and (Z)-1, which was remarkable in the case
of TMSOTf as a catalyst, also supports an SN2Ј mecha-
nism. One could expect that the transition state for the cy-
clization through an SN2Ј mechanism is facilitated for (E)-
1 in comparison to (Z)-1. In addition, the Thorpe–Ingold
substrates (E)-1h–(E)-1k underwent reaction faster than the
less branched analogues (E)-1a–(E)-1e. This again is in ac-
cordance with an SN2Ј mechanism, which involves a cycliza-
tion reaction along with simultaneous imidate substitution.
The Thorpe–Ingold effect should not significantly influence
the reaction rate of the SN1 mechanism where carbenium
ion formation is the rate-limiting step. It is actually possible
that both SN1 and SN2Ј mechanisms are operational. The
switch between these mechanistic pathways could explain
the different trans/cis ratios for compounds 2, depending on
the catalyst and configuration of substrates 1. On the basis
of these considerations, it can be hypothesized that using
Entry
R1
R2
Method
% Yield[a] 7[b]
1
2
3
4
5
n-pentyl
Bn
–CH2(CH2)3CH2–
–(CH2)2NBoc(CH2)2–
–(CH2)2O(CH2)2–
H
H
A
A
A
B
B
7a, 71
7c, 87
7i, 88
7j, 89
7k, 86
[a] Isolated yield. [b] Compounds 7a,[9] 7c,[10] and 7i[11] are known,
and their spectroscopic characterizations match with literature
data.
By using TMSOTf as an acid source, acidic hydrolysis
TMSOTf as a catalyst and starting with the (E) configura- conditions were applied to transform iminocarbonate 2b
into cyclic carbonate 8b (see Table 5, Entry 2). N-tosylcarb-
amates 1a and 1i were transformed into carbonates 8a and
8i, respectively, in a one-pot procedure. First, the cyclization
reactions of 1a and 1i were performed with TMSOTf as a
catalyst, and then water was added to achieve the hydrolysis
without isolation of the iminocarbonate intermediate. Also,
a one-pot procedure was tried with 10 mol-% BF3·Et2O and
substrate 1i. After the cyclization was complete, water was
added. However, no carbonate 8i formation was observed
after 16 h. Additional 10 mol-% of BF3·Et2O was added,
which resulted in approximately 7% formation of 8i after
1
8 h, according to H NMR analysis of the crude mixture.
Iminocarbonates are valuable substrates for halide ion-
promoted rearrangement to oxazolidinones.[6] To demon-
strate this, iminocarbonates trans-2a–trans-2c and 2i were
regioselectively rearranged into vinyl N-tosyloxazolidinones
trans-3a–trans-3c and 3i (see Table 6). More forcing condi-
tions were required for the transformation of branched
Figure 2. Hypothetical mechanisms for the formation of iminocar-
bonates 2.
iminocarbonate 2i into oxazolidinone 3i (see Table 6, En-
4
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Synthesis of Cyclic N-Tosyliminocarbonates
Table 5. Hydrolysis of iminocarbonates 2 to carbonates 8.
Experimental Section
General Remarks: The reagents and starting materials were ob-
tained from commercial sources and used as received. The solvents
were purified and dried by standard procedures prior to use, and
petroleum ether of a boiling range of 60–80 °C was used. All of
the reactions were performed under an argon atmosphere. Flash
chromatography was carried out using Merck Kieselgel (230–
400 mesh). Thin layer chromatography was performed on silica gel
and visualized by staining with KMnO4. The NMR spectroscopic
data were recorded with
a Varian Mercury spectrometer
(400 MHz). The chemical shifts values (δ) are given in ppm relative
to TMS with the residual chloroform signal as the internal stan-
dard. HRMS data were obtained with a Q-TOF micro high-resolu-
tion mass spectrometer with ESI (ESI+/ESI–). LC–MS analyses was
performed with a LC system Aliance separation module 2695 with
the mass selective detector Waters SQ3100. Olefins (E)- and (Z)-5
were synthesized in two steps from the corresponding aldehydes or
ketones as reported previously[5f] (see also Supporting Infor-
mation).
Entry
R1
R2
Substrate
% Yield[a] 8[b]
1
2
3
n-pentyl
iPr
–CH2(CH2)3CH2–
H
H
1a
trans-2b
1i
trans-8a, 67
trans-8b, 70
8i, 73
[a] Isolated yield. [b] Compounds 8a, 8b,[13] and 8i[14] are known,
and their spectroscopic characterizations match with literature
data.
General Procedure for Synthesis of Monotrichloroacetimidate 6: To
a solution of diol 5 (2.5 mmol) in CH2Cl2 (25 mL) were added mo-
lecular sieves (4 Å). The solution was cooled to 0 °C, and then
DBU (0.5 mmol, 20 mol-%) was added. The reaction mixture was
stirred at 0 °C for 30 min, and to this was added trichloroacetoni-
trile (2.5 mmol, 1 equiv.). The reaction mixture was stirred until
TLC indicated a complete conversion of the starting material (ca.
0.5–4 h). The solvent was removed, and the residue was purified by
flash column chromatography on silica gel eluting with a mixture of
light petroleum ether and EtOAc (4:1) to give monotrichloroacet-
imidate 6 as a colorless oil.
try 4). Oxazolidinones can easily be transformed into amino
alcohols. Thus, the cyclization of tosylcarbamates 1 fol-
lowed by rearrangement provides straightforward access to
valuable vinyl amino alcohol derivatives.[6,7,12]
Table 6. Rearrangement of iminocarbonates 2 to oxazolidinones 3.
(E)-4-Hydroxynon-2-enyl 2,2,2-Trichloroacetimidate [(E)-6a]: 1H
NMR (400 MHz, CDCl3): δ = 8.31 (s, 1 H, NH), 5.90–5.88 (m, 2
H, CH=CH), 4.80 (d, J = 4.3 Hz, 2 H, OCH2), 4.19–4.14 (m, 1 H,
CH), 1.59–1.55 [m, 8 H, (CH2)4CH3], 0.88 (t, J = 6.6 Hz, 3 H,
CH3) ppm. 13C NMR (100 MHz, CDCl3): δ = 162.48, 138.88,
123.48, 91.36, 72.10, 68.91, 37.02, 31.68, 24.96, 22.57, 13.99 ppm.
Unstable under conditions for HRMS.
Entry
R1
R2
Method
% Yield[a] 3[b]
1
2
3
4
n-pentyl
iPr
Bn
H
H
H
B
A
B
C
trans-3a, 73
trans-3b, 63
trans-3c, 74
3i, 85
(Z)-4-Hydroxynon-2-enyl 2,2,2-Trichloroacetimidate [(Z)-6a]: 1H
NMR (400 MHz, CDCl3): δ = 8.26 (s, 1 H, NH), 5.74 (dd, J =
–CH2(CH2)3CH2–
11.0 and 7.8 Hz,
1 H, CH=CHCH2), 5.67–5.61 (m, 1 H,
[a] Isolated yield. [b] Compounds 3a, 3b,[6b] and 3i[15] are known,
and their spectroscopic characterizations match with literature
data.
CH=CHCH2), 5.11 (dd, J = 12.5 and 8.2 Hz, 1 H, OCH2), 4.85
(dd, J = 12.5 and 6.7 Hz, 1 H, OCH2), 4.54–4.48 (m, 1 H, CH),
3.25 (d, J = 2.7 Hz, 1 H, OH), 1.66–1.26 [m, 8 H, (CH2)4CH3],
0.89 (t, J = 7.0 Hz, 3 H, CH3) ppm. 13C NMR (100 MHz, CDCl3):
δ = 162.89, 138.81, 123.57, 91.27, 67.58, 65.32, 36.85, 31.76, 24.93,
22.59, 14.01 ppm. Unstable under conditions for HRMS.
Conclusions
(E)-4-Hydroxy-5-methylhex-2-enyl 2,2,2-Trichloroacetimidate [(E)-
6b]: 1H NMR (400 MHz, CDCl3): δ = 8.32 (s, 1 H, NH), 5.94–5.85
(m, 2 H, CH=CH), 4.82 (d, J = 4.3 Hz, 1 H, OCH2), 3.93 (m, 1
H, CH), 1.72 [octet, J = 7.0 Hz, 1 H, CH(CH3)2], 0.93 [d, J =
6.7 Hz, 3 H, CH(CH3)2], 0.90 [d, J = 7.0 Hz, 3 H, CH(CH3)2] ppm.
13C NMR (100 MHz, CDCl3): δ = 162.44, 136.11, 124.46, 91.37,
68.87, 33.71, 18.11, 17.74 ppm. Unstable under conditions for
HRMS.
In summary, we have demonstrated that allylic trichloro-
acetimidates 1 bearing a δ-N-tosylcarbamoyloxy group un-
dergo intramolecular Lewis acid catalyzed allylic substitu-
tion to give cyclic N-tosyliminocarbonates 2. If substrates
with the (E) configuration are used in combination with
TMSOTf as a catalyst, the carbamates derived from sec-
ondary alcohols provided the highly selective formation of
trans-iminocarbonates. We also demonstrated the conver-
sion of iminocarbonates 2 into unsaturated 1,2-diols 7,
carbonates 8, and oxazolidinones 3. Thus, this methodology
based on Lewis acid catalyzed allylic substitution allows ef-
ficient access to these valuable products and avoids the use
of expensive and toxic late transition-metal catalysts.
(Z)-4-Hydroxy-5-methylhex-2-enyl 2,2,2-Trichloroacetimidate [(Z)-
6b]: 1H NMR (400 MHz, CDCl3): δ = 8.26 (s, 1 H, NH), 5.77
(dd, J = 11.3 and 7.8 Hz, 1 H, CH=CHCH2), 5.73–5.67 (m, 1 H,
CH=CHCH2), 5.11 (dd, J = 12.5 and 8.2 Hz, 1 H, OCH2), 4.87
(dd, J = 12.5 and 5.5 Hz, 1 H, OCH2), 4.22 (t, J = 7.1 Hz, 1 H,
CH), 3.25 (d, J = 2.7 Hz, 1 H, OH), 1.74 [octet, J = 6.7 Hz, 1 H,
CH(CH3)2], 0.97 [d, J = 6.7 Hz, 3 H, CH(CH3)2], 0.90 [d, J =
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5

Job/Unit: O20378
/KAP1
Date: 07-08-12 18:38:17
Pages: 11
L. Grigorjeva, A. Jirgensons
FULL PAPER
6.7 Hz, 3 H, CH(CH3)2] ppm. 13C NMR (100 MHz, CDCl3): δ =
162.90, 137.03, 124.40, 91.27, 72.58, 65.44, 33.60, 18.05 ppm. Un-
stable under conditions for HRMS.
J = 15.7 Hz, 1 H, HC=CHCH2), 5.87 (dt, J = 15.7 and 5.5 Hz, 1
H, HC=CHCH2), 4.80 (dd, J = 5.9 and 1.2 Hz, 2 H, OCH2), 1.35
[s, 6 H, C(CH3)2] ppm. 13C NMR (100 MHz, CDCl3): δ = 162.53,
142.64, 120.09, 91.38, 70.58, 69.15, 29.58 ppm. Unstable under con-
ditions for HRMS.
(E)-4-Hydroxy-5-phenylpent-2-enyl 2,2,2-Trichloroacetimidate [(E)-
6c]: 1H NMR (400 MHz, CDCl3): δ = 8.31 (s, 1 H, NH), 7.33–7.21
(m, 5 H, C6H5), 5.97 (dd, J = 15.7 and 5.1 Hz, 1 H, CH=CHCH2),
5.90 (dt, J = 15.7 and 5.1 Hz, 1 H, CH=CHCH2), 4.80 (d, J =
5.1 Hz, 2 H, OCH2), 4.45–4.39 (m, 1 H, CH), 2.90 (dd, J = 13.7
and 5.1 Hz, 1 H, CH2Ph), 2.80 (dd, J = 13.7 and 8.2 Hz, 1 H,
CH2Ph), 1.72 (d, J = 3.9 Hz, 1 H, OH) ppm. 13C NMR (100 MHz,
CDCl3): δ = 162.45, 137.33, 136.37, 129.55, 128.54, 126.67, 123.87,
91.37, 72.50, 68.77, 43.82 ppm. HRMS (EI): calcd. for
C13H14Cl3NO2Na [M + Na]+ 343.9988; found 344.0009.
(E)-3-(1-Hydroxycyclohexyl)allyl 2,2,2-Trichloroacetimidate [(E)-
1
6i]: H NMR (400 MHz, CDCl3): δ = 8.27 (s, 1 H, NH), 5.98 (d,
J = 16.0 Hz, 1 H, HC=CHCH2), 5.90 (dt, J = 15.7 and 5.5 Hz, 1
H, HC=CHCH2), 4.80 (d, J = 5.5 Hz, 2 H, OCH2), 1.67–1.20 [m,
10 H, CH2(CH2)3CH2] ppm. 13C NMR (100 MHz, CDCl3): δ =
162.49, 142.59, 120.62, 91.41, 71.26, 69.31, 37.66, 25.39, 21.90 ppm.
Unstable under conditions for HRMS.
(E)-3-[1-(tert-Butoxycarbonyl)-4-hydroxypiperidin-4-yl]allyl 2,2,2-
Trichloroacetimidate [(E)-6j]: 1H NMR (400 MHz, CDCl3): δ =
8.31 (s, 1 H, NH), 5.94–5.92 (m, 2 H, CH=CH), 4.81 (d, J = 4.3 Hz,
2 H, OCH2), 3.89–3.81 [m, 2 H, CH2N(Boc)], 3.24–3.18 [m, 2 H,
CH2N(Boc)], 1.71–1.49 [m, 4 H, CH2CH2N(Boc)CH2CH2], 1.45 [s,
9 H, C(CH3)3] ppm. 13C NMR (100 MHz, CDCl3): δ = 162.42,
154.73, 141.24, 121.63, 91.30, 79.49, 69.68, 68.85, 36.80, 28.43 ppm.
HRMS (EI): calcd. for C15H23Cl3N2O4Na [M + Na]+ 423.0582;
found 423.0621.
(E)-4-Hydroxytetradeca-2,13-dienyl 2,2,2-Trichloroacetimidate [(E)-
6d]: 1H NMR (400 MHz, CDCl3): δ = 8.31 (s, 1 H, NH), 5.93–5.87
(m, 2 H, CH=CH), 5.80 (ddt, J = 17.2, 10.2, and 6.7 Hz, 1 H,
CH=CH2), 4.98 (d, J = 17.2 Hz, 1 H, CH2=CH), 4.92 (d, J =
10.2 Hz, 1 H, CH2=CH), 4.80 (d, J = 3.9 Hz, 2 H, CH2O), 4.16
(br. s, 1 H, OH), 2.04 (q, J = 6.7 Hz, 2 H, CH2=CHCH2), 1.64–
1.24 [m, 14 H, (CH2)7] ppm. 13C NMR (100 MHz, CDCl3): δ =
162.48, 139.18, 137.88, 123.46, 114.11, 91.37, 72.08, 68.91, 37.05,
33.78, 29.48, 29.47, 29.37, 29.08, 28.89, 25.28 ppm. Unstable under
conditions for LC–MS and HRMS.
(E)-3-(4-Hydroxytetrahydro-2H-pyran-4-yl)allyl
2,2,2-Trichloro-
acetimidate [(E)-6k]: 1H NMR (400 MHz, CDCl3): δ = 8.33 (s, 1
H, NH), 5.98 (d, J = 16.0 Hz, 1 H, CH=CHCH2), 5.92 (dt, J =
15.6 and 5.1 Hz, 1 H, CH=CHCH2), 4.82 (d, J = 4.7 Hz, 2 H,
CH2O), 3.85–3.72 (m, 4 H, CH2OCH2), 1.87–1.80 (m, 2 H,
CH2CH2OCH2CH2), 1.57–1.52 (m, 2 H, CH2CH2OCH2CH2) ppm.
13C NMR (100 MHz, CDCl3): δ = 162.43, 141.35, 121.58, 91.31,
68.89, 68.87, 63.55, 37.60 ppm. Unstable under conditions for
HRMS.
(E)-4-Hydroxy-5,5-diphenylpent-2-enyl 2,2,2-Trichloroacetimidate
[(E)-6e]: 1H NMR (400 MHz, CDCl3): δ = 8.22 (s, 1 H, NH), 7.38–
7.15 (m, 10 H, C6H5), 5.94–5.83 (m, 2 H, CH=CH), 4.92 (dt, J =
8.2 and 3.9 Hz, 1 H, CHO), 4.71 (d, J = 4.3 Hz, 2 H, OCH2) 4.98
(d, J = 8.6 Hz, 1 H, CHPh2), 1.80 (d, J = 3.9 Hz, 1 H, OH) ppm.
13C NMR (100 MHz, CDCl3): δ = 162.27, 141.26, 140.60, 135.00,
128.78, 128.77, 128.57, 128.55, 126.99, 126.70, 124.73, 91.31, 73.73,
68.60, 58.63 ppm. Unstable under conditions for LC–MS. HRMS
(EI): calcd. for C19H18Cl3NO2Na [M + Na]+ 420.0301; found
420.0335.
General Procedure for Synthesis of N-Tosylcarbamate 1: To a solu-
tion of monotrichloroacetimidate 6 (2 mmol) in THF (20 mL) were
added molecular sieves (4 Å). The reaction mixture was cooled to
0 °C, and then TsNCO (2 mmol, 1 equiv.) was added dropwise. The
solution was stirred at room temperature until TLC indicated the
complete conversion of the starting material (ca. 2 h). The solvent
was removed, and the residue was purified by flash column
chromatography on silica gel eluting with a mixture of light petro-
leum ether and EtOAc (2:1) to give tosylcarbamate 1 as a colorless
oil.
(E)-4-Hydroxy-4-phenylbut-2-enyl 2,2,2-Trichloroacetimidate [(E)-
6f]: 1H NMR (400 MHz, CDCl3): δ = 8.32 (s, 1 H, NH), 7.39–7.27
(m, 5 H, C6H5), 6.09 (dd, J = 15.7 and 5.5 Hz, 1 H, CH=CHCH2),
6.01 (dt, J = 15.7 and 5.5 Hz, 1 H, CH=CHCH2), 5.27 (t, J =
3.9 Hz, 1 H, CH), 4.83 (d, J = 5.5 Hz, 2 H, OCH2), 2.12 (d, J =
3.9 Hz, 1 H, OH) ppm. 13C NMR (100 MHz, CDCl3): δ = 162.46,
142.23, 136.42, 128.62, 127.91, 126.35, 124.09, 91.30, 74.21,
68.72 ppm. Unstable under conditions for HRMS.
(E)-4-(Tosylcarbamoyloxy)non-2-enyl
2,2,2-Trichloroacetimidate
(Z)-4-Hydroxy-4-phenylbut-2-enyl 2,2,2-Trichloroacetimidate [(Z)-
6f]: 1H NMR (400 MHz, CDCl3): δ = 8.33 (s, 1 H, NH), 7.42–7.27
(m, 5 H, C6H5), 5.96 (dd, J = 11.0 and 7.8 Hz, 1 H, CH=CHCH2),
5.77–5.70 (m, 1 H, CH=CHCH2), 5.64 (dd, J = 7.4 and 2.3 Hz, 1
H, CH), 5.23 (dd, J = 12.5 and 8.2 Hz, 1 H, OCH2), 5.00 (dd, J =
12.5 and 5.9 Hz, 1 H, OCH2), 3.74 (d, J = 2.7 Hz, 1 H, OH) ppm.
13C NMR (100 MHz, CDCl3): δ = 162.94, 142.53, 137.89, 128.57,
127.61, 126.0, 123.64, 91.23, 69.92, 65.25 ppm. Unstable under con-
ditions for HRMS.
1
[(E)-1a]: H NMR (400 MHz, CDCl3): δ = 8.33 (s, 1 H, C=NH),
7.90 (d, J = 8.6 Hz, 2 H, C6H4Me), 7.40 (br. s, 1 H, NHTs), 7.33
(d, J = 8.2 Hz, 2 H, C6H4Me), 5.81 (dt, J = 15.7 and 5.1 Hz, 1 H,
CH=CHCH2), 5.70 (dd, J = 15.7 and 6.7 Hz, 1 H, CH=CHCH2),
5.14 (q, J = 6.7 Hz, 1 H, CH), 4.74 (d, J = 5.5 Hz, 2 H, OCH2),
2.45 (s, 3 H, C6H4CH3), 1.63–1.50 [m, 2 H, CH2(CH2)3CH3], 1.28–
1.11 [m, 6 H, CH2(CH2)3CH3], 0.84 [t, J = 6.7 Hz, 3 H, CH2(CH2)3-
CH3] ppm. 13C NMR (100 MHz, CDCl3): δ = 162.28, 149.76,
144.99, 135.63, 131.16, 129.56, 128.33, 126.58, 91.22, 77.11, 68.14,
34.04, 31.32, 24.36, 22.39, 21.67, 13.89 ppm. HRMS (EI): calcd.
for C19H25Cl3N2O5SNa [M + Na]+ 521.0447; found 521.0396.
(E)-4-Hydroxy-4-(4-methoxyphenyl)but-2-enyl 2,2,2-Trichloroacet-
imidate [(E)-6g]: 1H NMR (400 MHz, CDCl3): δ = 8.31 (s, 1 H,
NH), 7.28 (d, J = 8.6 Hz, 2 H, C6H4), 6.88 (d, J = 8.6 Hz, 2 H,
C6H4), 6.07 (dd, J = 15.3 and 5.1 Hz, 1 H, HC=CHCH2), 5.98 (dt,
J = 15.3 and 5.5 Hz, 1 H, HC=CHCH2), 5.22 (t, J = 3.9 Hz, 1 H,
CH), 4.82 (d, J = 5.1 Hz, 2 H, OCH2), 3.80 (s, 3 H, OCH3) ppm.
13C NMR (100 MHz, CDCl3): δ = 162.47, 159.30, 136.63, 134.47,
127.72, 123.72, 113.99, 91.32, 73.74, 68.79, 55.28 ppm. Unstable
under conditions for HRMS.
(Z)-4-(Tosylcarbamoyloxy)non-2-enyl
2,2,2-Trichloroacetimidate
1
[(Z)-1a]: H NMR (400 MHz, CDCl3): δ = 8.30 (s, 1 H, C=NH),
7.90 (d, J = 8.2 Hz, 2 H, C6H4Me), 7.53 (br. s, 1 H, NHTs), 7.33
(d, J = 8.2 Hz, 2 H, C6H4Me), 5.77 (dt, J = 11.0 and 6.7 Hz, 1 H,
CH=CHCH2), 5.51–5.37 (m, 2 H, CHCH=CHCH2), 4.91 (dd, J =
12.9 and 6.7 Hz, 1 H, OCH2), 4.83 (dd, J = 12.9 and 6.7 Hz, 1 H,
OCH2), 2.45 (s, 3 H, C6H4CH3), 1.69–1.45 [m, 2 H, CH2(CH2)3-
CH3], 1.30–1.15 [m, 6 H, CH2(CH2)3CH3], 0.85 [t, J = 6.7 Hz, 3 H,
CH2(CH2)3CH3] ppm. 13C NMR (100 MHz, CDCl3): δ = 162.32,
(E)-4-Hydroxy-4-methylpent-2-enyl 2,2,2-Trichloroacetimidate [(E)-
1
6h]: H NMR (400 MHz, CDCl3): δ = 8.31 (s, 1 H, NH), 6.01 (d,
6
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O20378
/KAP1
Date: 07-08-12 18:38:17
Pages: 11
Synthesis of Cyclic N-Tosyliminocarbonates
149.67, 145.00, 135.61, 131.73, 129.57, 128.32, 127.17, 91.17, 73.66, 91.10, 77.56, 67.71, 55.88, 21.64 ppm. Unstable under conditions
64.90, 34.27, 31.43, 24.36, 22.41, 21.67, 13.92 ppm. HRMS (EI):
calcd. for C19H25Cl3N2O5SNa [M
521.0396.
for LC–MS.
+
Na]+ 521.0447; found
(E)-4-Phenyl-4-(tosylcarbamoyloxy)but-2-enyl 2,2,2-Trichloroacet-
imidate [(E)-1f]: 1H NMR (400 MHz, CDCl3): δ = 8.34 (s, 1 H,
C=NH), 7.88 (d, J = 8.6 Hz, 2 H, C6H4Me), 7.34–7.27 (m, 5 H,
C6H4Me and C6H5), 7.22–7.20 (m, 2 H, C6H5), 6.15 (d, J = 5.7 Hz,
1 H, CH), 5.96 (dd, J = 15.7 and 5.5 Hz, 1 H, CH=CHCH2), 5.87
(dt, J = 15.7 and 5.5 Hz, 1 H, CH=CHCH2), 4.78 (d, J = 5.1 Hz,
2 H, OCH2), 2.44 (s, 3 H, C6H4CH3) ppm. 13C NMR (100 MHz,
CDCl3): δ = 162.26, 149.62, 144.90, 137.21, 135.48, 130.66, 129.61,
129.52, 128.56, 128.22, 127.02, 126.34, 91.09, 77.91, 68.05,
21.60 ppm. HRMS (EI): calcd. for C20H19Cl3N2O5SNa [M +
Na]+ 526.9978; found 527.0172.
(E)-5-Methyl-4-(tosylcarbamoyloxy)hex-2-enyl 2,2,2-Trichloroacet-
imidate [(E)-1b]: 1H NMR (400 MHz, CDCl3): δ = 8.33 (s, 1 H,
C=NH), 7.90 (d, J = 8.2 Hz, 2 H, C6H4Me), 7.69 (br. s, 1 H,
NHTs), 7.33 (d, J = 8.6 Hz, 2 H, C6H4Me), 5.75 (dt, J = 15.7 and
5.1 Hz, 1 H, CH=CHCH2), 5.67 (dd, J = 15.7 and 6.3 Hz, 1 H,
CH=CHCH2), 4.97 (t, J = 6.3 Hz, 1 H, CH), 4.73 (d, J = 4.7 Hz,
2 H, OCH2), 2.44 (s, 3 H, C6H4CH3), 1.83 [octet, J = 6.7 Hz, 1 H,
CH(CH3)2], 0.82 [d, J = 7.0 Hz, 6 H, CH(CH3)2] ppm. 13C NMR
(100 MHz, CDCl3): δ = 162.22, 149.81, 144.98, 135.65, 129.58,
129.29, 128.26, 127.41, 91.23, 81.57, 68.05, 31.92, 21.66, 17.75,
17.64 ppm. HRMS (EI): calcd. for C17H21Cl3N2O5SNa [M +
Na]+ 493.0134; found 493.0158.
(Z)-4-Phenyl-4-(tosylcarbamoyloxy)but-2-enyl 2,2,2-Trichloroacet-
imidate [(Z)-1f]: 1H NMR (400 MHz, CDCl3): δ = 8.32 (s, 1 H,
C=NH), 7.88 (d, J = 8.2 Hz, 2 H, C6H4Me), 7.35–7.27 (m, 7 H,
C6H4Me and C6H5), 6.45 (d, J = 8.6 Hz, 1 H, CH), 5.88–5.76 (m,
2 H, CH=CH), 4.99 (dd, J = 13.3 and 6.3 Hz, 1 H, OCH2), 4.92
(Z)-5-Methyl-4-(tosylcarbamoyloxy)hex-2-enyl 2,2,2-Trichloroacet-
imidate [(Z)-1b]: 1H NMR (400 MHz, CDCl3): δ = 8.30 (s, 1 H,
C=NH), 7.90 (d, J = 8.6 Hz, 2 H, C6H4Me), 7.33 (d, J = 8.2 Hz,
2 H, C6H4Me), 5.83 (dt, J = 11.3 and 6.6 Hz, 1 H, CH=CHCH2),
5.46 (dd, J = 11.3 and 9.8 Hz, 1 H, CH=CHCH2), 5.18 (dd, J =
9.4 and 6.6 Hz, 1 H, CH), 4.93–4.82 (m, 2 H, OCH2), 2.45 (s, 3 H,
C6H4CH3), 1.84 [octet, J = 6.7 Hz, 1 H, CH(CH3)2], 0.85 [d, J =
6.6 Hz, 6 H, CH(CH3)2] ppm. 13C NMR (100 MHz, CDCl3): δ =
162.35, 149.80, 144.95, 135.67, 129.69, 129.56, 128.23, 91.16, 77.79,
65.06, 32.06, 21.66, 17.81, 17.66 ppm. HRMS (EI): calcd. for
C17H21Cl3N2O5SNa [M + Na]+ 493.0134; found 493.0089.
(dd,
J = 13.3 and 5.9 Hz, 1 H, OCH2), 2.44 (s, 3 H,
C6H4CH3) ppm. 13C NMR (100 MHz, CDCl3): δ = 162.30, 149.46,
145.05, 137.55, 135.47, 131.05, 129.59, 128.71, 128.57, 128.32,
127.17, 126.66, 91.09, 74.45, 64.82, 21.67 ppm. HRMS (EI): calcd.
for C20H19Cl3N2O5SNa [M + Na]+ 526.9978; found 526.9928.
(E)-4-Methyl-4-(tosylcarbamoyloxy)pent-2-enyl 2,2,2-Trichloroacet-
imidate [(E)-1h]: 1H NMR (400 MHz, CDCl3): δ = 8.31 (s, 1 H,
C=NH), 7.88 (d, J = 8.6 Hz, 2 H, C6H4Me), 7.33 (d, J = 8.2 Hz,
2 H, C6H4Me), 6.00 (d, J = 16.0 Hz, 1 H, CH=CHCH2), 5.76 (dt,
J = 16.0 and 5.5 Hz, 1 H, CH=CHCH2), 4.75 (d, J = 5.5 Hz, 2 H,
OCH2), 2.45 (s, 3 H, C6H4CH3), 1.49 [s, 6 H, C(CH3)2] ppm. 13C
NMR (100 MHz, CDCl3): δ = 162.33, 148.62, 144.85, 139.40,
137.27, 129.53, 128.23, 122.93, 91.24, 83.25, 68.55, 26.38,
21.67 ppm. HRMS (EI): calcd. for C16H19Cl3N2O5SNa [M +
Na]+ 478.9978; found 479.0020.
(E)-5-Phenyl-4-(tosylcarbamoyloxy)pent-2-enyl 2,2,2-Trichloroacet-
imidate [(E)-1c]: 1H NMR (400 MHz, CDCl3): δ = 8.31 (s, 1 H,
C=NH), 7.86 (d, J = 8.2 Hz, 2 H, C6H4Me), 7.71 (br. s, 1 H,
NHTs), 7.31 (d, J = 8.2 Hz, 2 H, C6H4Me), 7.23–7.17 (m, 3 H,
CH2C6H5), 7.07–7.05 (m, 2 H, CH2C6H5), 5.78–5.69 (m, 2 H,
CH=CH), 5.39–5.34 (m, 1 H, CH), 4.69 (d, J = 2.7 Hz, 2 H,
OCH2), 2.92 (dd, J = 14.0 and 7.0 Hz, 1 H, CH2Ph), 2.84 (dd, J =
14.0 and 6.3 Hz, 1 H, CH2Ph), 2.45 (s, 3 H, C6H4CH3) ppm. 13C
NMR (100 MHz, CDCl3): δ = 162.21, 149.48, 145.00, 135.53,
135.49, 130.01, 129.58, 129.52, 128.35, 128.29, 126.93, 126.76,
91.17, 77.05, 67.94, 40.63, 21.67 ppm. HRMS (EI): calcd. for
C21H21Cl3N2O5SNa [M + Na]+ 541.0134; found 541.0145.
(E)-3-[1-(Tosylcarbamoyloxy)cyclohexyl]allyl 2,2,2-Trichloroacet-
imidate [(E)-1i]: 1H NMR (400 MHz, CDCl3): δ = 8.29 (s, 1 H,
C=NH), 7.88 (d, J = 8.2 Hz, 2 H, C6H4Me), 7.48 (br. s, 1 H,
NHTs), 7.33 (d, J = 8.2 Hz, 2 H, C6H4Me), 5.94 (d, J = 16.0 Hz,
1
H, CH=CHCH2), 5.64 (dt, J = 16.0 and 5.9 Hz, 1 H,
CH=CHCH2), 4.70 (d, J = 5.5 Hz, 2 H, OCH2), 2.45 (s, 3 H,
C6H4CH3), 2.15–2.08 [m, 2 H, CH2(CH2)3CH2], 1.58–1.44 [m, 8 H,
CH2(CH2)3CH2] ppm. 13C NMR (100 MHz, CDCl3): δ = 162.25,
148.42, 144.80, 136.67, 135.90, 129.55, 128.12, 126.45, 123.90,
91.27, 84.57, 68.63, 34.89, 24.99, 21.67, 21.60 ppm. HRMS (EI):
calcd. for C19H24Cl3N2O5S [M + H]+ 497.0472; found 497.0449.
(E)-4-(Tosylcarbamoyloxy)tetradeca-2,13-dienyl
2,2,2-Trichloro-
acetimidate [(E)-1d]: 1H NMR (400 MHz, CDCl3): δ = 8.33 (s, 1
H, C=NH), 7.90 (d, J = 8.2 Hz, 2 H, C6H4Me), 7.56 (br. s, 1 H,
NHTs), 7.33 (d, J = 8.2 Hz, 2 H, C6H4Me), 5.86–5.67 (m, 3 H,
CH=CH, CH2=CH), 5.14 (q, J = 7.6 Hz, 1 H, CHO), 5.98 (d, J =
17.2 Hz, 1 H, CH2=CH), 4.92 (d, J = 10.2 Hz, 1 H, CH2=CH),
4.74 (d, J = 5.5 Hz, 2 H, CH2O), 2.44 (s, 3 H, CH3), 2.03 (q, J =
(E)-3-[1-(tert-Butoxycarbonyl)-4-(tosylcarbamoyloxy)piperidin-4-yl]-
allyl 2,2,2-Trichloroacetimidate [(E)-1j]: 1H NMR (400 MHz,
CDCl3): δ = 8.30 (s, 1 H, C=NH), 7.86 (d, J = 8.6 Hz, 2 H,
C6H4Me), 7.68 (br. s, 1 H, NHTs), 7.34 (d, J = 8.2 Hz, 2 H,
C6H4Me), 5.96 (d, J = 16.0 Hz, 1 H, CH=CHCH2), 5.67 (dt, J =
16.0 and 5.5 Hz, 1 H, CH=CHCH2), 4.71 (d, J = 5.5 Hz, 2 H,
OCH2), 3.82–3.68 [m, 2 H, CH2N(Boc)CH2], 3.10–2.95 [m, 2 H,
CH2N(Boc)CH2], 2.45 (s, 3 H, C6H4CH3), 2.15–2.09 [m, 2 H,
CH2CH2N(Boc)CH2CH2], 1.71–1.63 [m, 2 H, CH2CH2N(Boc)-
CH2CH2], 1.41 [s, 9 H, C(CH3)3] ppm. 13C NMR (100 MHz,
CDCl3): δ = 162.16, 154.54, 148.39, 145.04, 135.79, 134.94, 129.65,
128.00, 125.02, 91.15, 82.15, 79.83, 68.22, 34.28, 28.38, 21.68 ppm.
HRMS (EI): calcd. for C23H30Cl3N3O7SNa [M + Na]+ 620.0768;
found 620.0828.
6.1 Hz, 2 H, CH2CH=CH2), 1.63–1.10 [m, 14 H, (CH2)7] ppm. 13
C
NMR (100 MHz, CDCl3): δ = 162.27, 149.69, 145.01, 139.12,
135.61, 131.12, 129.57, 128.35, 126.65, 114.16, 91.23, 77.15, 68.11,
34.09, 33.76, 29.34, 29.31, 29.18, 29.04, 28.86, 24.72, 21.68 ppm.
Unstable under conditions for LC–MS.
(E)-5,5-Diphenyl-4-(tosylcarbamoyloxy)pent-2-enyl 2,2,2-Trichloro-
acetimidate [(E)-1e]: 1H NMR (400 MHz, CDCl3): δ = 8.22 (s, 1
H, C=NH), 7.75 (d, J = 8.2 Hz, 2 H, C6H4Me), 7.26 (d, J = 7.8 Hz,
2 H, C6H4Me), 7.23–7.08 (m, 10 H, C6H5), 5.94 (dd, J = 9.4,
6.3 Hz, 1 H, CHCHPh), 5.77 (dt, J = 15.7 and 4.7 Hz, 1 H,
CH=CHCH2), 5.68 (dd, J = 15.7 and 6.3 Hz, 1 H, CH=CHCH2),
4.61 (d, J = 4.7 Hz, 2 H, OCH2), 4.10 (d, J = 9.8 Hz, 1 H, CHPh),
2.45 (s, 3 H, C6H4CH3) ppm. 13C NMR (100 MHz, CDCl3): δ = (E)-3-[4-(Tosylcarbamoyloxy)tetrahydro-2H-pyran-4-yl]allyl 2,2,2-
161.98, 149.65, 144.73, 139.93, 139.70, 135.42, 129.49, 129.44,
128.58, 128.54, 128.37, 128.06, 128.05, 127.57, 126.95, 126.65,
Trichloroacetimidate [(E)-1k]: 1H NMR (400 MHz, CDCl3): δ =
8.32 (s, 1 H, C=NH), 7.86 (d, J = 8.2 Hz, 2 H, C6H4Me), 7.81 (br.
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Job/Unit: O20378
/KAP1
Date: 07-08-12 18:38:17
Pages: 11
L. Grigorjeva, A. Jirgensons
FULL PAPER
s, 1 H, NHTs), 7.34 (d, J = 8.2 Hz, 2 H, C6H4Me), 5.98 (d, J =
16.0 Hz, 1 H, CH=CHCH2), 5.70 (dt, J = 16.0 and 5.5 Hz, 1 H,
= 7.8 Hz, 1 H, CHCHCH2), 2.37 (s, 3 H, CH3), 2.00 (q, J = 7.0 Hz,
2 H, CH2=CHCH2), 1.76–1.64 (m, 2 H, CH2CH), 1.42–1.21 [m, 12
CH=CHCH2), 4.74 (d, J = 5.5 Hz, 2 H, OCH2), 3.68 (dt, J = 11.7 H, (CH2)6] ppm. 13C NMR (100 MHz, CDCl3): δ = 159.23, 143.14,
and 3.9 Hz, 2 H, CH2OCH2), 3.63–3.57 (m, 2 H, CH2OCH2), 2.45 138.90, 138.25, 130.31, 129.07, 127.06, 122.76, 114.07, 85.64, 85.15,
(s, 3 H, C6H4CH3), 2.11–2.08 (m, 2 H, CH2CH2OCH2CH2), 1.89– 33.59, 33.04, 29.10, 29.05, 28.85, 28.68, 24.38, 21.39 ppm. LC–MS
1.82 (m, 2 H, CH2CH2OCH2CH2) ppm. 13C NMR (100 MHz, (ESI): m/z = 406.28 [M + H]+. HRMS (EI): calcd. for C22H32NO4S
CDCl3): δ = 162.17, 148.47, 145.00, 135.83, 134.98, 129.63, 128.01, [M + H]+ 406.2052; found 406.2057.
125.15, 91.16, 81.39, 68.23, 63.26, 35.13, 21.67 ppm. HRMS (EI):
calcd. for C18H21Cl3N2O6SNa [M
521.0143.
trans-4-Diphenylmethyl-2-tosylimino-5-vinyl-1,3-dioxolane (2e): 1H
+
Na]+ 521.0084; found
NMR (400 MHz, CDCl3): δ = 7.75 (d, J = 8.4 Hz, 2 H, C6H4Me),
7.33–7.23 (m, 10 H, C6H5), 7.17 (d, J = 7.9 Hz, 2 H, C6H4Me),
5.57 (ddd, J = 16.8, 10.1, and 6.6 Hz, 1 H, CH2=CH), 5.21 (d, J =
10.1 Hz, 1 H, CH2=CH), 5.19 (t, J = 7.5 Hz, 1 H, CHCHPh), 5.12
(d, J = 16.8 Hz, 1 H, CH2=CH), 4.93 (t, J = 7.1 Hz, 1 H,
CHCH=CH2), 4.18 (d, J = 7.9 Hz, 1 H, CHPh), 2.38 (s, 3 H,
CH3) ppm. 13C NMR (100 MHz, CDCl3): δ = 158.86, 143.17,
138.09, 137.94, 137.88, 130.41, 129.12, 129.10, 128.88, 128.48,
128.40, 127.95, 127.61, 127.29, 121.86, 85.95, 84.15, 53.70, 21.49
ppm. LC–MS (ESI): m/z = 434.20 [M + H]+.
General Procedure for Synthesis of Iminocarbonate 2: Molecular
sieves (4 Å) and the Lewis acid catalyst (0.05 mmol, 10 mol-%)
were added to a stirred solution of tosylcarbamate 1 (0.50 mmol)
in DCM (dichloromethane, 10 mL) at room temperature. After the
reaction was complete (as indicated by TLC), the solvent was re-
moved under reduced pressure. The residue was purified by
chromatography on a short silica gel column eluting with a mixture
of light petroleum ether and EtOAc (2:1) to afford product 2 as an
oil.
Compound 2g: This product was crystallized from EtOAc; m.p.
trans-4-Pentyl-2-tosylimino-5-vinyl-1,3-dioxolane (2a): 1H NMR
(400 MHz, CDCl3): δ = 7.85 (d, J = 8.2 Hz, 2 H, C6H4CH3), 7.26
(d, J = 8.2 Hz, 2 H, C6H4CH3), 5.83 (ddd, J = 17.2, 10.6, and
7.0 Hz, 1 H, CH=CH2), 5.50 (d, J = 16.0 Hz, 1 H, CH=CH2),
5.46 (d, J = 10.2 Hz, 1 H, CH=CH2), 4.81 (t, J = 7.4 Hz, 1 H,
CH2=CHCH), 4.46 (q, J = 5.1 Hz, 1 H, CHCH2CH2), 2.40 (s, 3
H, C6H4CH3), 1.79–1.67 [m, 2 H, CH2(CH2)3CH3], 1.48–1.20 [m,
6 H, CH2(CH2)3CH3], 0.87 [t, J = 6.7 Hz, 3 H, CH2(CH2)3-
CH3] ppm. 13C NMR (100 MHz, CDCl3): δ = 159.23, 143.21,
138.54, 130.39, 129.15, 127.14, 122.87, 85.64, 85.19, 32.12, 31.07,
24.16, 22.23, 21.46, 13.80 ppm. HRMS (EI): calcd. for
C17H24NO4S [M + H]+ 338.1426; found 338.1447.
trans-4-Isopropyl-2-tosylimino-5-vinyl-1,3-dioxolane (2b): 1H NMR
(400 MHz, CDCl3): δ = 7.85 (d, J = 8.4 Hz, 2 H, C6H4CH3), 7.27
(d, J = 8.4 Hz, 2 H, C6H4CH3), 5.83 (ddd, J = 17.2, 10.1, and
7.0 Hz, 1 H, CH=CH2), 5.50 (d, J = 16.8 Hz, 1 H, CH=CH2),
5.46 (d, J = 10.6 Hz, 1 H, CH=CH2), 4.92 (t, J = 7.0 Hz, 1 H,
CH2=CHCH), 4.27 [t, J = 7.0 Hz, 1 H, CHCH(CH3)2], 2.41 (s, 3
H, C6H4CH3), 1.99 [octet, J = 6.6 Hz, 1 H, CH(CH3)2], 0.98 [d, J
= 6.6 Hz, 3 H, CH(CH3)2], 0.94 [d, J = 6.6 Hz, 3 H, CH-
(CH3)2] ppm. 13C NMR (100 MHz, CDCl3): δ = 159.14, 143.18,
138.47, 131.38, 129.16, 127.20, 122.33, 89.38, 83.49, 31.16, 21.50,
17.19, 17.16 ppm. HRMS (EI): calcd. for C15H19NO4SNa [M +
Na]+ 332.0932; found 332.0948.
trans-4-Benzyl-2-tosylimino-5-vinyl-1,3-dioxolane (2c): 1H NMR
(400 MHz, CDCl3): δ = 7.77 (d, J = 8.4 Hz, 2 H, C6H4CH3), 7.28–
7.12 (m, 5 H, C6H4CH3 and C6H5), 7.12 (d, J = 7.9 Hz, 2 H, C6H5),
5.66 (ddd, J = 17.6, 10.6, and 7.1 Hz, 1 H, CH=CH2), 5.32 (d, J =
10.6 Hz, 1 H, CH=CH2), 5.30 (d, J = 16.8 Hz, 1 H, CH=CH2),
4.88 (t, J = 7.5 Hz, 1 H, CH2=CHCH), 4.70 (q, J = 7.5 Hz, 1 H,
CHBn), 3.12 (dd, J = 14.5 and 7.9 Hz, 1 H, CH2C6H5), 3.02 (dd,
J = 14.5 and 5.7 Hz, 1 H, CH2C6H5), 2.38 (s, 3 H, C6H4CH3) ppm.
13C NMR (100 MHz, CDCl3): δ = 159.11, 143.33, 138.30, 133.15,
130.22, 129.48, 129.24, 129.00, 127.76, 127.21, 122.57, 85.03, 84.60,
37.81, 21.50 ppm. HRMS (EI): calcd. for C19H20NO4S [M + H]+
358.1113; found 358.1125.
124–125 °C.
4,4-Dimethyl-2-tosylimino-5-vinyl-1,3-dioxolane (2h): 1H NMR
(400 MHz, CDCl3): δ = 7.86 (d, J = 8.6 Hz, 2 H, C6H4CH3), 7.27
(d, J = 8.4 Hz, 2 H, C6H4CH3), 5.78 (ddd, J = 17.2, 10.2, and
6.7 Hz, 1 H, CH=CH2), 5.52 (d, J = 16.8 Hz, 1 H, CH=CH2), 5.49
(d, J = 10.6 Hz, 1 H, CH=CH2), 4.82 (d, J = 7.0 Hz, 1 H, CH),
2.41 (s, 3 H, C6H4CH3), 1.56 [s, 3 H, C(CH3)2], 1.33 [s, 3 H,
C(CH3)2] ppm. 13C NMR (100 MHz, CDCl3): δ = 158.65, 143.13,
138.65, 129.15, 127.95, 127.17, 122.88, 88.32, 80.43, 25.29, 21.81,
21.53 ppm. HRMS (EI): calcd. for C14H17NO4SNa [M + Na]+
318.0776; found 318.0754.
2-Tosylimino-4-vinyl-1,3-dioxaspiro[4.5]decane (2i): 1H NMR
(400 MHz, CDCl3): δ = 7.85 (d, J = 8.1 Hz, 2 H, C6H4CH3), 7.26
(d, J = 8.5 Hz, 2 H, C6H4CH3), 5.76 (ddd, J = 17.1, 10.0, and
6.6 Hz, 1 H, CH=CH2), 5.47 (d, J = 17.3 Hz, 1 H, CH=CH2), 5.46
(d, J = 10.3 Hz, 1 H, CH=CH2), 4.75 (d, J = 6.8 Hz, 1 H, CH),
2.40 (s, 3 H, CH3), 1.92–1.20 [m, 10 H, CH2(CH2)3CH2] ppm. 13C
NMR (100 MHz, CDCl3): δ = 158.75, 143.09, 138.66, 129.15,
128.16, 127.18, 122.50, 90.37, 88.50, 34.73, 31.01, 24.46, 21.95,
21.49, 21.35 ppm. HRMS (EI): calcd. for C17H22NO4S [M + H]+
336.1270; found 336.1241.
8-(tert-Butoxycarbonyl)-2-tosylimino-4-vinyl-1,3-dioxa-8-azaspiro-
[4.5]decane (2j): 1H NMR (400 MHz, CDCl3): δ = 7.85 (d, J =
8.6 Hz, 2 H, C6H4Me), 7.28 (d, J = 8.2 Hz, 2 H, C6H4Me), 5.76
(ddd, J = 17.2, 10.2, and 7.0 Hz, 1 H, CH=CH2), 5.53 (d, J =
16.8 Hz, 1 H, CH=CH2), 5.51 (d, J = 10.2 Hz, 1 H, CH=CH2),
4.80 (d, J = 7.0 Hz, 1 H, CH), 4.09–3.94 [m, 2 H, CH2N(Boc)CH2],
3.12–2.89 [m, 2 H, CH2N(Boc)CH2], 2.41 (s, 3 H, C6H4CH3), 1.91–
1.58 [m,
4
H, CH2CH2N(Boc)CH2CH2], 1.44 [s,
9
H,
C(CH3)3] ppm. 13C NMR (100 MHz, CDCl3): δ = 158.12, 154.25,
143.37, 138.44, 129.27, 127.47, 127.16, 123.29, 88.03, 84.90, 80.30,
33.98, 30.78, 28.33, 21.52 ppm. HRMS (EI): calcd. for
C21H29N2O6S [M + H]+ 437.1746; found 437.1751.
2-Tosylimino-4-vinyl-1,3,8-trioxaspiro[4.5]decane (2k): 1H NMR
(400 MHz, CDCl3): δ = 7.86 (d, J = 8.2 Hz, 2 H, C6H4Me), 7.29 (d,
J = 8.2 Hz, 2 H, C6H4Me), 5.77 (ddd, J = 17.2, 10.6, and 7.0 Hz, 1
H, CH=CH2), 5.55 (d, J = 17.0 Hz, 1 H, CH=CH2), 5.52 (d, J =
10.6 Hz, 1 H, CH=CH2), 4.81 (d, J = 6.7 Hz, 1 H, CH), 3.90–3.58
J = 7.8 Hz, 2 H, C6H4Me), 5.85–5.71 (m, 2 H, (m, 4 H, CH2OCH2), 2.41 (s, 3 H, C6H4CH3), 1.94–1.67 (m, 4
trans-4-(Dec-9-en-1-yl)-2-tosylimino-5-vinyl-1,3-dioxolane (2d): 1H
NMR (400 MHz, CDCl3): δ = 7.81 (d, J = 8.2 Hz, 2 H, C6H4Me),
7.24 (d,
CH2=CHCH and CH2=CHCH2), 5.46 (d, J = 18.0 Hz, 1 H, H, CH2CH2OCH2CH2) ppm. 13C NMR (100 MHz, CDCl3): δ =
CH2=CHCH), 5.43 (d, J = 10.6 Hz, 1 H, CH2=CHCH), 4.95 (d, J
= 16.8 Hz, 1 H, CH2=CHCH2), 4.89 (d, J = 10.2 Hz, 1 H,
CH2=CHCH2), 4.80 (t, J = 7.4 Hz, 1 H, CHCH=CH2), 4.47 (q, J
158.16, 143.33, 138.47, 129.25, 127.50, 127.16, 123.25, 88.15, 88.03,
63.49, 63.21, 34.45, 31.38, 21.51 ppm. HRMS (EI): calcd. for
C16H19NO5SNa [M + Na]+ 360.0882; found 360.0914.
8
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O20378
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Date: 07-08-12 18:38:17
Pages: 11
Synthesis of Cyclic N-Tosyliminocarbonates
General Procedure for Synthesis of Diol 7
General Procedure for the Rearrangement leading to Vinyloxazolidi-
none 3: LiI (0.6 mmol, 1.2 equiv., Methods A or C) or TBAB (tetra-
butylammonium bromide, 0.6 mmol, 1.2 equiv., Method B) was
added to a stirred solution of iminocarbonate 2 (0.5 mmol) in
C2H4Cl2 (10 mL, Methods A or B) or DMF (dimethylformamide,
Method C). The reaction mixture was refluxed for approximately
2 h, until the complete conversion of starting material was achieved
(as monitored by TLC). The mixture was cooled to room tempera-
ture, and the solvent was removed under reduced pressure. The
residue was purified by chromatography on a silica gel column elut-
ing with a mixture of light petroleum ether and ethyl acetate (3:1)
to afford product 3. Compounds 3a, 3b,[7b] and 3i[15] have been
described previously in literature.
Method A: To a solution of iminocarbonate 2 (0.3 mmol) in MeOH
(5 mL) was added NaOH (1 m aqueous solution, 5 mL), and the
resulting mixture was stirred overnight at room temperature. After
the reaction was complete (as monitored by TLC), the MeOH was
removed under reduced pressure. The residue was neutralized with
HCl (1 m aqueous solution) to pH ≈ 7, and the resulting solution
was extracted with CH2Cl2 (3ϫ10 mL). The organic layers were
combined and washed with brine. The organic phase was dried with
Na2SO4, filtered, and concentrated. The residue was purified by
chromatography on a silica gel column eluting with a mixture of
light petroleum ether and ethyl acetate (from 4:1 to 2:1) to afford
product 7.
(4,5-trans)-5-Benzyl-3-tosyl-4-vinyloxazolidin-2-one (3c): 1H NMR
(400 MHz, CDCl3): δ = 7.82 (d, J = 8.4 Hz, 2 H, C6H4CH3), 7.34–
7.16 (m, 7 H, C6H4CH3 and C6H5), 5.75 (ddd, J = 17.0, 8.8, and
6.6 Hz, 1 H, CH=CH2), 5.30 (d, J = 10.1 Hz, 1 H, CH=CH2), 5.28
(d, J = 17.0 Hz, 1 H, CH=CH2), 4.55 (dd, J = 7.9 and 4.2 Hz, 1
H, CHCH=CH2), 4.39 (ddd, J = 10.4, 6.2, and 4.1 Hz, 1 H,
CHBn), 3.02 (dd, J = 14.3 and 6.2 Hz, 1 H, CH2Ph), 2.93 (dd, J =
14.3 and 6.2 Hz, 1 H, CH2Ph), 2.44 (s, 3 H, C6H4CH3) ppm. 13C
NMR (100 MHz, CDCl3): δ = 151.21, 145.38, 134.89, 133.84,
133.78, 129.64, 129.47, 128.87, 128.44, 127.45, 120.30, 80.11, 63.22,
39.24, 21.68 ppm. HRMS (EI): calcd. for C19H20N2O4S [M +
Na]+ 358.1113; found 358.1098.
Method B: To iminocarbonate 2 (0.3 mmol) was added K2CO3
(0.5 m solution) in MeOH/H2O (1:1, 5 mL), and the resulting mix-
ture was stirred at room temperature. After the reaction was com-
plete (as monitored by TLC), the solvent was removed under re-
duced pressure. The residue was purified by chromatography on a
silica gel column eluting with a mixture of light petroleum ether
and ethyl acetate (from 4:1 to 2:1) to afford the product 7. Com-
pounds 7a,[9] 7c,[10] and 7i[11] have been described previously in lit-
erature.
1-(tert-Butoxycarbonyl)-4-hydroxy-4-(1-hydroxyallyl)piperidine (7j):
1H NMR (400 MHz, CDCl3): δ = 5.91 (ddd, J = 17.2, 10.2, and
6.7 Hz, 1 H, CH=CH), 5.31 (d, J = 17.2 Hz, 1 H, CH=CH2), 5.28
(d, J = 10.2 Hz, 1 H, CH=CH2), 3.99–3.87 [m, 2 H, CH2N(Boc)-
CH2], 3.86 (d, J = 7.0 Hz, 1 H, CH), 3.17–3.08 [m, 2 H, CH2N-
(Boc)CH2], 2.12 (br. s, 1 H and 1 H, 2 OH), 1.67–1.47 [m, 4 H,
CH2CH2N(Boc)CH2CH2], 1.45 [s, 9 H, C(CH3)3] ppm. 13C NMR
(100 MHz, CDCl3): δ = 154.81, 135.94, 118.60, 79.49, 79.42, 71.44,
33.66, 31.87, 28.44 ppm. HRMS (EI): calcd. for C13H23NO4Na [M
+ Na]+ 280.1525; found 280.1473.
Supporting Information (see footnote on the first page of this arti-
cle): Synthesis and characterization of (E)- and (Z)-5, NMR spec-
tra of intermediates and final products, X-ray ORTEP drawing of
2i.
Acknowledgments
4-(1-Hydroxyallyl)tetrahydro-2H-pyran-4-ol (7k): 1H NMR
(400 MHz, CDCl3): δ = 5.91 (ddd, J = 17.2, 10.2, and 7.0 Hz, 1 H,
CH=CH2), 5.31 (d, J = 17.2 Hz, 1 H, CH=CH2), 5.27 (d, J =
10.1 Hz, 1 H, CH=CH2), 3.84 (d, J = 7.0 Hz, 1 H, CH), 3.80–3.70
(m, 4 H, CH2OCH2), 2.44 (br. s, 1 H, OH), 1.93 (br. s, 1 H, OH),
1.76–1.56 (m, 3 H, CH2CH2OCH2CH2), 1.45–1.39 (m, 1 H,
CH2CH2OCH2CH2) ppm. 13C NMR (100 MHz, CDCl3): δ =
135.87, 118.54, 79.58, 70.56, 63.50, 63.30, 34.45, 32.74 ppm. Un-
stable under conditions for HRMS.
Financial support from the European Regional Development Fond
(grant number ERAF 2010/2DP/2.1.1.1.0./10/APIA/ VIAA/074) is
gratefully acknowledged. We thank Dr. M. Petrova for performing
2D NMR experiments and A. Maleckis for assistance in the manu-
script preparation.
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1996, 96, 395–422; b) B. M. Trost, M. L. Crawley, Chem. Rev.
2003, 103, 2921–2944; c) Z. Lu, S. Ma, Angew. Chem. 2008,
120, 264; Angew. Chem. Int. Ed. 2008, 47, 258–297.
General Procedure for Synthesis of Carbonate 8
[2] a) U. Jana, S. Maiti, S. Biswas, Tetrahedron Lett. 2008, 49, 858–
862; b) N. Kawai, R. Abe, J. I. Uenishi, Tetrahedron Lett. 2009,
50, 6580–6583; c) A. Guérinot, A. Serra-Muns, C. Gnamm, C.
Bensoussan, S. Reymond, J. Cossy, Org. Lett. 2010, 12, 1808–
1811; d) S. Hanessian, T. Focken, R. Oza, Tetrahedron 2011,
67, 9870–9884; e) A. Guérinot, A. Serra-Muns, C. Bensoussan,
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Method A: Trimethylsilyl trifluoromethanesulfonate (0.05 mmol,
10 mol-%) and H2O (10 μL) were added to a stirred solution of
iminocarbonate 2 (0.5 mmol) in CH2Cl2 (10 mL) at room tempera-
ture. After the reaction was complete (as monitored by TLC), the
solvent was removed under reduced pressure. The residue was puri-
fied by chromatography on a silica gel column eluting with a mix-
ture of light petroleum ether and ethyl acetate (from 4:1 to 2:1) to
afford product 8.
Method B: Trimethylsilyl trifluoromethanesulfonate (0.08 mmol,
10 mol-%) was added to a stirred solution of tosylcarbamate 1
(0.8 mmol) in CH2Cl2 (15 mL) at room temperature. After reaction
was complete (as indicated by TLC), H2O (10 μL) was added, and
then the reaction mixture was stirred at room temperature until the
full conversion of intermediate 2 was observed (indicated by TLC).
The solvent was removed under reduced pressure, and the residue
was purified by chromatography on a silica gel column eluting with
a mixture of light petroleum ether and ethyl acetate (from 4:1 to
2:1) to afford product 8. Compounds 8a, 8b,[13] and 8i[14] have been
described previously in literature.
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Date: 07-08-12 18:38:17
Pages: 11
L. Grigorjeva, A. Jirgensons
FULL PAPER
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[8] In the view of one of the referees of this article, the selective
formation of iminocarbonates versus oxazolines can be ex-
plained by better the leaving group ability of the Lewis acid
Received: March 26, 2012
Published Online: ᭿
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Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O20378
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Date: 07-08-12 18:38:17
Pages: 11
Synthesis of Cyclic N-Tosyliminocarbonates
Allylic Substitution
L. Grigorjeva, A. Jirgensons* ......... 1–11
Synthesis of Cyclic N-Tosyliminocarb-
onates by Lewis Acid Catalyzed Allylic
Substitution of Trichloroacetimidates
Keywords: Synthetic methods / Nitrogen
heterocycles / Nucleophilic substitution /
Cyclization / Lewis acids / Allylic com-
pounds
N-Tosyliminocarbonates were prepared by
a Lewis acid catalyzed cyclization of allylic
trichloroacetimidates bearing a δ-N-tosyl-
carbamoyloxy group. The synthetic utility
of iminocarbonates was demonstrated by
transforming them into 1,2-diols, cyclic
carbonates, and N-tosyloxazolidinones.
Eur. J. Org. Chem. 0000, 0–0
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