Oxidative sulfamidation of vinyl silanes: A route to diverse silylated N-Heterocycles

Article abstract of DOI:10.1016/j.tet.2019.06.045

The reaction of trimethyl(vinyl)silane 1 and dimethyl(divinyl)silane 2 with various sulfonamides in the oxidative system (tert-BuOCl + NaI) has been studied and shown to be an efficient approach for the synthesis of silylated N-heterocycles. Triflamide demonstrated the reactivity principally different from that of arenesulfonamides. With silane 1, it afforded the products of iodochlorination and bis(triflamidation) (major), whereas arenesulfonamides gave N-arenesulfonylaziridines in up to 91% yield. Silane 2 with arenesulfonamides yielded the products of mono and bis(iodochlorination), mono and bis(aziridination), and 3,5-diiodo-4,4-dimethyl-1-(arylsulfonyl)-1,4-azasilinanes. By contrast, triflamide, apart from the products of halogenation and iodotriflamidation, unexpectedly gave 3-(trifluoromethylsulfonyl)-5-(triflamido)oxazolidine as the main product. The structure of most heterocyclic products is proved by X-ray analysis. The effect of the silyl group in the substrate and of the substituent in the reagent on the course of oxidative sulfamidation is discussed by comparing with all-carbon analogues.

Full text of DOI:10.1016/j.tet.2019.06.045

Accepted Manuscript
Oxidative sulfamidation of vinyl silanes: A route to diverse silylated N-Heterocycles
Vera V. Astakhova, Bagrat A. Shainyan, Mikhail Yu. Moskalik, Irina V. Sterkhova
PII:
S0040-4020(19)30717-3
https://doi.org/10.1016/j.tet.2019.06.045
TET 30437
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 21 May 2019
Revised Date: 25 June 2019
Accepted Date: 27 June 2019
Please cite this article as: Astakhova VV, Shainyan BA, Moskalik MY, Sterkhova IV, Oxidative
sulfamidation of vinyl silanes: A route to diverse silylated N-Heterocycles, Tetrahedron (2019), doi:
https://doi.org/10.1016/j.tet.2019.06.045.
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ACCEPTED MANUSCRIPT
Oxidative Sulfamidation of Vinyl Silanes: A Route to Diverse Silylated N-Heterocycles
Vera V. Astakhova, Bagrat A. Shainyan,* Mikhail Yu. Moskalik, Irina V. Sterkhova
ABSTRACT: The reaction of trimethyl(vinyl)silane
1
and dimethyl(divinyl)silane
2
with
various sulfonamides in the oxidative system (tert-BuOCl + NaI) has been studied and
shown to be an efficient approach for the synthesis of silylated N-heterocycles. Triflamide
demonstrated the reactivity principally different from that of arenesulfonamides. With
silane
1, it afforded the products of iodochlorination and bis(triflamidation) (major),
whereas arenesulfonamides gave N-arenesulfonylaziridines in up to 91% yield. Silane
2
with arenesulfonamides yielded the products of mono and bis(iodochlorination), mono
and bis(aziridination), and 3,5-diiodo-4,4-dimethyl-1-(arylsulfonyl)-1,4-azasilinanes. By
contrast, triflamide, apart from the products of halogenation and iodotriflamidation,
unexpectedly gave 3-(trifluoromethylsulfonyl)-5-(triflamido)oxazolidine as the main
product. The structure of most heterocyclic products is proved by X-ray analysis. The
effect of the silyl group in the substrate and of the substituent in the reagent on the course
of oxidative sulfamidation is discussed by comparing with all-carbon analogues.
Keywords: sulfonamides · vinyl silanes · oxidative sulfonamidation · aziridines · 1,4-
azasilinanes · reaction mechanisms
1. Introduction
The reactions of oxidative sulfamidation of alkenes1-4 and dienes5-10 is a mild metal-free method
for the synthesis of unsaturated sulfonamides and various N-heterocycles.11-13 Unsaturated
triflamide derivatives (N-allyl- and N,N-diallyltriflamide) have also been examined as substrates
in these reactions and showed the formation of different linear, cyclic and bicyclic products in
the ratio depending on the reagents and reaction conditions.14 Oxidative sulfamidation of
* A.E. Favorsky Irkutsk Institute of Chemistry, Siberian Division of Russian Academy of
Sciences 664033 Irkutsk, Russia.
E-mail: bagrat@irioch.irk.ru

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heterodienes is confined to the reactions of triflamide with diallyl sulfide,15 divinyl sulfoxide and
divinyl sulfone.16 The first substrate affords the sulfur atom oxidation products, first acyclic λ4-
sulfane, N,N'-(diprop-2-en-1-yl-λ4-sulfanediyl)bis(triflamide), (CF3SO2NH)2S(CH2CH=CH2)2.
The latter two reactions proceed as heterocyclization resulting in 2,6-diiodo-4-
(trifluoromethylsulfonyl)thiomorpholine 1-oxide or 1,1-dioxide.
There are very few studies on the reactions of sulfonamidation of vinyl silanes. In early
works, free-radical addition of N,N-dichloroarylsulfonamides to vinyl- and allylsilanes was
studied.17,18 The addition of TsNCl2 to vinyl- and allylsilanes proceeds with different regio-
selectivity leading to Me3SiCH(Cl)CH2N(Cl)Ts and Me3SiCH2C[N(Cl)Ts]CH2Cl, respectively;17
replacement of hydrogens and/or methyls in Me3SiCH=CH2 by chlorine hinders the reaction.18
4-Silacyclopentenes undergo aziridination with chloramine-T in the presence of ammonium
tribromide salt.19 Nucleophilic ring opening of the formed aziridines followed by deprotection
provides an efficient and stereoselective route to unnatural cyclic sila-substituted β-amino acids.
Scheme 1. Aziridination of 4-silacyclopentanes with Chloramine T.
The first reaction which can be considered as oxidative sulfamidation of unsaturated
silanes was the reaction of 3-silylated cyclohexa-1,4-dienes with chloramines in water or aqueous-
organic media in the presence of K2OsO4 as an oxidant.20 The reaction occurs at only one double
bond with the major adduct having the sulfonamide residue closer to the silyl group.
Scheme 2. Diastereo- and regioselective hydroxysulfamidation of 3-dialkylsilylcyclohexa-1,4-
dienes with Chloramines.
The Rh-catalyzed oxidative intramolecular sulfamidation of 4-silylated (3Z)-but-3-en-1-yl
sulfamates proceeds with different stereoselectivity for achiral and chiral substrates (Scheme 3).21

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Scheme 3. Intramolecular aziridination of achiral and chiral silylvinyl sulfamates.
Therefore, one can conclude that no reactions of electrophilic oxidative sulfamidation of
unsaturated silanes are known; at the same time, vinyl silanes must be active as substrates in
electrophilic sulfamidation due to the stabilizing effect of silicon on β-carbocations. In this paper
we report the first study of the reactions of oxidative sulfamidation of trimethyl(vinyl)silane 1
and dimethyl(divinyl)silane 2 [and, for comparison, diphenyl(divinyl)silane] with sulfonamides.
Apart from fundamental interest in the chemistry of unsaturated silanes and functionalized
sulfonamides, the products of the investigated reactions containing pharmacophoric sulfonamide
group and silicon atom may show biological activity. Bioisosteric replacement is a promising
molecular design approach successfully used in medicinal chemistry, and the C and Si atoms are
classical bioisosteres.22-27 A lot of nitrogen-containing heterocycles, including those possessing
silylated groups in the molecule, display biological activity, that attracts the attention of
researchers.28–31
2. Results and discussion
The reaction of trimethyl(vinyl)silane 1 with sulfonamides CF3SO2NH2 (TfNH2, 3) and
XC6H4SO2NH2 [X = H (4a), Me (4b), Cl (4c), NO2 (4d)] was performed at different temperatures
using a 1:1.5 ratio of the reagents amide:silane in the presence of oxidative system (t-BuOCl +
NaI). This system was successfully used by us for oxidative sulfamidation of alkenes and
dienes.1-10, 14-16
Silane 1 reacts with triflamide 3 at 10–15°С or –30°С to afford a whole bunch of products
of oxidative addition, the main ones being (2-chloro-1-iodoethyl)trimethylsilane 5 and N,N'-[1-
(trimethylsilyl)ethane-1,2-diyl]bis(triflamide) 6. Also, N-[2-iodo-2-(trimethylsilyl)ethyl]triflamide
7 and N-[2-chloro-1-(trimethylsilyl)ethyl]triflamide 8 were isolated by column chromatography
from the ethereal–hexane eluate as an inseparable mixture of minor products 7:8 = 4:3 in 4–13%
total yield. 2-Iodo-2-(trimethylsilyl)ethanol 9 was isolated from the hexane eluate in trace
amounts (Scheme 4). Different regiochemistry of the products of halotriflamidation 7 and 8 is

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proved by different splitting of the NH proton in the 1H NMR spectrum – triplet in 7 and doublet
in 8, and can be rationalized by different routes of their formation (see Scheme 6 below). The
conversion of triflamide increases on cooling from 86 to 98%, as does the total yield from 64 to
78%, apparently due to lower amount of side products at lower temperature.
Scheme 4. Oxidative triflamidation/halogenation of silane 1.
Arenesulfonamides 4 react with silane 1 in the temperature range from –30 to +45 ºC in a
different manner (Scheme 5) resulting in adduct 5 as a minor product and 1-(arylsulfonyl)-2-
(trimethylsilyl)aziridines 10a–d in up to 91% yield (Table 1). The structure of aziridine 10d was
proved by X-ray analysis (Fig. 1).
Scheme 5. Iodochlorination and aziridination of silane 1 with arenesulfonamides 4a–d.
Figure 1. Molecular structure of aziridine 10d.

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Table 1. Conversion and isolated yields of products 5 and 10 (Scheme 5)
Yield, %
X in
Conversion
of amide, %
Temperature, ºC
p-XC6H4SO2NH2
5
10
47
71
31
86
84
91
45
15
86
89
32
98
95
98
31
19
16
13
11
6
H
–30
15
CH3
Cl
15
NO2
15
A tentative mechanism of formation of all products in Schemes 4 and 5 can be proposed as
follows (Scheme 6). The structure of compounds 5, 7 and 9 is consistent with the ring opening in
the intermediate iodonium cation from the side of less sterically hindered CH2 group.
Scheme 6. Tentative mechanism of the reaction of trimethyl(vinyl)silane 1 with triflamide 3 and
arenesulfonamides 4.
Although the formation of intermediate iodonium cation in Scheme 6 is fully consistent
with the formation of products 5 and 7 as the precursors of 6 and 8, the formation of products 6
and 8 via an independent pathway, through the aziridinium intermediate, cannot be completely
ruled out. The ‘aziridinium’ mechanism was proposed in a series of works on reactions of
TsNCl2 with electron-deficient alkenes leading to the products of deamination32-35 or aziridines.36
The reaction of dimethyl(divinyl)silane 2 with sulfonamides 3 and 4a–d was performed
under the same conditions as those for silane 1. The reaction of silane 2 with triflamide proceeds
in high total yield as shown in Scheme 7. The main product is 3-(trifluoromethylsulfonyl)-5-
(triflamido)oxazolidine 11, the product of iodotriflamidation 12 is formed in lower yield, and
very small amounts of the products of mono- and bis(iodochlorination) 13 and 14 were isolated.

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Scheme 7. Oxidative triflamidation/halogenation of dimethyl(divinyl)silane 2. Reaction
conditions: solvent MeCN, –30°С, 24 h, 2:3 = 1:1. The yields with respect to the converted
triflamide are the isolated yields after column chromatography.
While the products of iodotriflamidation and iodochlorination 12–14 in Scheme 7 are
similar to those obtained earlier and can be expected to be formed, the formation of oxazolidine
11 is surprising since it implies desilylation and the cleavage of the C=C double bond of
substrate 2. The reaction of formation of product 11 is easily balanced assuming the formation of
silanol Me3SiOH 15 (which can be further transformed into siloxane Me3SiOSiMe3), as follows:
The mechanism of formation of oxazolidine 11 is not clear and deserves special study. Its
structure only presumes that one Si–C bond and one of the initially double C=C bonds in 2 are
split, apparently hydrolytically, as schematically shown in Scheme 8.
I
Me
t-BuOI
Me
Me
Me
Me
I+
t-BuOI
Si
2
2 TfNH2
OH-
Si
NTf
-t-BuOH, -HI
Si
NTf
Me
-t-BuOH, -HI
NHTf
TfNH
NHTf
NHTf
I
OH
NTf
Me
Me
Tf
N
Me
Me
I
H2O
O
Si
Si
OH
TfNH
NHTf
16
Me3SiOSiMe3
11
TfNH2
-TfNHI
16
Me3SiOH
15
-H2OI
Scheme 8. Tentative mechanism of formation of 3-(trifluoromethylsulfonyl)-5-(triflamido)-
oxazolidine 11 via desilylation and the C=C double bond cleavage of dimethyl(divinyl)silane 2.
The structure of oxazolidine 11 was proved by NMR spectroscopy, in particular by the
presence of two CF3 quartets, one methine and two methylene groups in the 13C NMR spectrum,

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and the corresponding proton signals, which were assigned based on Jmod, 1H–1H and 1H–13C 2D
1
NMR spectra. The H and 13C NMR spectra of products 12, 13 show diastereotopic methyl
signals, and compound 14 is formed as two diastereomers in the ratio of 5:4. The formation of
silanols 15, 16 and, apparently, the corresponding siloxanes after their dehydration is confirmed
1
by the presence of a number of signals in the 0–1 ppm region of the H NMR spectrum of the
reaction mixture.
This unusual reactivity is not specific for silane 2, because the formation of product 11 was
found also in the reaction of diphenyl(divinyl)silane 17 with triflamide under the same
conditions. However, it is specific for triflamide as a sulfamidating reagent, since no analogues
of oxazolidine 11 or the product of iodotriflamidation 12 were obtained from the reactions of
silane 2 with arenesulfonamides 4a–d. Instead, the reaction of 2 with sulfonamides 4 gives rise
to the formation of the products of aziridination 18–20 and 1,4-azasilinanes 21 (Scheme 9). The
only products identical to those formed in the reaction with triflamide (Scheme 7) were the
products of iodochlorination 13 and 14. The reaction conditions and the yields of the products
are summarized in Table 2.
Scheme 9. Oxidative sulfonamidation/halogenation/aziridination of dimethyl(divinyl)silane 2 with
arenesulfonamides 4. Reaction conditions: solvent MeCN, –30°С, 24 h, 2:4 = 1:1. The yields with respect
to the converted arenesulfonamides are the isolated yields after column chromatography.
Table 2. Products of the reaction of dimethyl(divinyl)silane 2 with arenesulfonamides 4 (Scheme 9).[a]
Product yields[b]
Conversion of
Entry Sulfonamide
sulfonamide, %
19 (dr)[c]
20 (dr)[c, d]
13
28
27
14
23
26
14
5
18
13
7
21
4
1
2
3
4
5
49
84
85
58
66
25 (65:35) 21 (44:56)
4a
4b
3
29 (67:33) 15 (49:51)
4
2
4.5[e] 55 (61:39) 11 (42:58)
4
4c
3
54
42
12 (69:31)
26
–
–
2
4d
4d[f]
6
–
[a] Reaction conditions: solvent MeCN, –30°С, 24 h, 2:4 = 1:1. [b] After column chromatography. [c] dr
1
– diastereomeric ratio from relative intensities of the SiMe signals in the H NMR spectra. [d]
RS:(RR+SS) ratio. [e] Yield determined by 1H NMR spectroscopy. [f] 2:4d = 2:1.

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Oxazolidine 11 and 1,4-azasilinanes 21 are crystalline compounds, whereas the adducts 13,
14, and aziridines 18–20 are viscous light-yellow oils, slowly solidified upon standing.
The structure of the products of aziridination 18–20 was proved by NMR spectroscopy, in
1
13
particular, by the presence of diastereotopic methyl signals in the H and C NMR spectra, the
formation of diastereomers of compounds 19 and 20 in different ratio, and by the values of 1JCH
coupling constants falling in the range 170–190 Hz typical for aziridines.7,37
Mono and diaziridines 19 and 20 are formed as diastereomeric mixtures as proved by the
presence of two sets of signals both in the 1H and 13C NMR spectra, the ratios are given in Table
2. The SiMe groups in monoaziridines 19 show two signals for each diastereomer, whereas
symmetrical diaziridines 20 show two signals of one diastereomer and one signal of the second
diastereomer, which allows to assign them, respectively, to the (R,R+S,S)- and R,S-diastereomer
(meso-form). Symmetrical products 21 existing in the R,S-form (see Figure 3 and Figures SI-3–
SI-6) show two SiMe signals due to the axial and equatorial methyls on the azasilinane ring.
For compound 18d and for all 1,4-azasilinanes 21a–d the molecular structure was also
ascertained by X-ray structural analysis (Figures 2, 3).
Figure 2. Molecular structure of 2-[1,1-dimethyl(vinyl)silyl]-1-[(4-nitrophenyl)sulfonyl]aziridine
18d. The terminal olefinic methylene group is disordered over two conformations in 55:45 ratio.
Figure 3. Molecular structure of 3,5-diiodo-4,4-dimethyl-1-(phenylsulfonyl)-1,4-azasilinane
21a. Molecular structures of its analogues 21b–d are very similar (see Supporting Information).
Note, that azasilinanes 21a–d are formed as meso-diastereomers having the iodine atoms in
the equatorial positions. The structure of compounds 12–14, 19a–d, 21a–d having the iodine
atoms in the α-position to silicon is consistent with the initial electrophilic iodination of

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divinylsilanes 2 and 17. The MP2/6-31G* theoretical calculations38 showed that the maximum of
the electron density in 2 or 17 is located on the internal olefinic CH groups (–0.25e), while the
terminal CH2 groups are practically uncharged (<0.01e). Therefore, the electrophilic attack by
iodonium ion must be directed on the internal atoms of the double bonds.
The probable mechanism of the reaction, assuming the presence in the reaction mixture of
various species containing the O–I and I–Cl bonds and capable of iodination and chlorination of
the double bonds,39 is outlined in Scheme 10.
Scheme 10. Tentative mechanism of the formation of products of the reaction of
dimethyl(divinyl)silane 2 with triflamide 3 and arenesulfonamides 4.
To confirm the mechanism in Scheme 10, additional experiments were performed using
sulfonamide 4d as the reagent in the same oxidative system (t-BuOCl+NaI). Thus, when product
13 was introduced in the reaction with 4d, diadduct 14 (37%) and aziridine 19d (16%), were
obtained. In the reaction of 4d with aziridine 18d, the already known product 19d and the
diaziridine 20d lacking in the reaction of 4d with silane 2 were formed in the yield of 80% and
20%, respectively (from 1H NMR analysis) (Scheme 11).
Scheme 11. The products of the reaction of nosylamide 4d with monoadduct 13 and
monoaziridine 18d in the oxidative system (t-BuOCl+NaI).
It would be interesting to compare the reactivity of silanes 1 and 2 with their all-carbon
analogues, that is, 3,3-dimethylbutene-1 and 3,3-dimethylpentadiene-1,4. Unfortunately, the two
are rarely used as substrates in the reactions of oxidative amidation; thus, for the latter diene we
failed to find any examples of such reactions. As to 3,3-dimethylbutene-1, it is aziridinated with

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PhI=NTs in the presence of different Cu-based catalysts in up to 90% yield.40-42 It also reacts
with H2NSO3CH2CCl3 in the presence of PhI=O and Cu(dibenzoylmethanoate) complexes with
N-heterocyclic carbenes,43 or with TsNH2 in the presence of excess PhI(OAc)2, I2 and t-BuOK to
give the corresponding aziridines in moderate yield.44 It could be assumed that in the latter work
the aziridine is formed via elimination of HI from the intermediate adduct RCH(NHTs)CH2I
(which was indeed obtained by the reaction of styrene with PhI=NTs) but the authors showed
that it does not cyclize to aziridine under the action of t-BuOK.44 No formation of the products
of hydroxyamination or haloamination analogous to products 7 or 8 in Scheme 4 was reported
for the reactions of oxidative sulfamidation of 3,3-dimethylbutene-1, although the α-amino-β-
chloro derivatives can be obtained by the ring opening of N-arylsulfonyl-2-tBu-substituted
aziridines with Me3SiCl catalyzed by chiral 1,2,3-triazolium chlorides.45
Therefore, silane 1 shows the reactivity different from its all-carbon analogue: with
arenesulfonamides the latter gives only aziridines, whereas silane 1 yields also the product of
dihalogenation 5 (Scheme 5). Even more striking dissimilarity was shown for the reaction with
triflamide, which gave no aziridine but, instead, the products of dihalogenation, bis-
triflamidation, and halotriflamidation with different regioselectivity (Scheme 4).
3. Conclusions
To summarize, we have studied for the first time the oxidative sulfonamidation of
trimethylvinylsilane, dimethyl(divinyl)silane and diphenyl(divinyl)silane with triflamide and
arenesulfonamides. In the system (t-BuOCl+NaI), the reactions of dimethyl(divinyl)silane 2 with
arenesulfonamides were shown to give the products of iodochlorination, aziridination and
heterocyclization to 1,4-azasilinanes in high total yield. In the same conditions, triflamide
reacted with divinylsilanes in a different manner. Both with dimethyl(divinyl)silane and
diphenyl(divinyl)silane, the reaction occurred with the rupture of the Si–Csp2 and C=C bonds and
formation of the same main product, 3-(trifluoromethylsulfonyl)-5-(triflamido)oxazolidine. The
main product of the reaction of trimethylvinylsilane 1 with triflamide was linear adduct, N,N'-[1-
(trimethylsilyl)ethane-1,2-diyl)bis(triflamide), whereas arenesulfonamides react with silane 1 via
aziridination of the double bond. Therefore, the reaction with silane 2 is not selective but,
instead, it allowed to demonstrate diverse reactivity in the reactions of oxidative sulfonamidation
leading to numerous and sometimes unexpected products. In contrast, the reactions of oxidative
arenesulfonamidation of silane 1 provide a convenient synthetic route to silylated N-arylsulfonyl-
aziridines in up to 91% isolated yield. Apart from the demonstrated diverse reactivity patterns,
the novelty of this work is the synthesis of more than twenty new compounds, which belong to
potentially biologically active silylated N-heterocycles and, thus, deserve further investigation.

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4. Experimental Section
4.1. General
All starting materials reported in the manuscript have been previously described in literature. All
1
products were identified using H NMR and 13C analysis and comparison with authentic
1
samples. IR spectra were taken on a Bruker Vertex 70 spectrophotometer in KBr. H NMR and
13C NMR spectra were recorded in CDCl3 and CD3CN on Bruker DPX 400 spectrometer at
working frequencies 400 (1H), 100 (13C), 40.5 (15N), 79.5 (29Si) and 376 (19F) MHz. All shifts are
reported in parts per million (ppm) relative to residual CHCl3 peak (7.27 and 77.2 ppm, 1H NMR
13
1
and C NMR, respectively) and CD3CN peak (1.95 (1H), 1.3 and 118 (13C) ppm, H NMR and
13C NMR, respectively). All coupling constants (J) are reported in hertz (Hz). Abbreviations are:
s, singlet; d, doublet; t, triplet; q, quartet; brs, broad singlet. Melting point was measured on
MeltEMP (laboratory devices). All flash chromatography was performed using silica gel, 60 Å,
300 mesh. TLC analysis was carried out on aluminum plates coated with silica gel 60 F254, 0.2
mm thickness. The plates were visualized using a 254 nm ultraviolet lamp or aqueous NaIO4
1
solutions. H NMR and 13C NMR, IR and X-Ray data are given for all compounds in the
Supporting Experimental.
4.2 Synthesis
4.2.1 Reaction of triflamide with vinyltrimethylsilane in the system t-BuOCl+NaI. To the
solution of (2.00 g, 13 mmol) of triflamide and (6.04 g, 40 mmol) of NaI in 80 ml of CH3CN
(2.01 g, 20 mmol) of vinyltrimethylsilane was added, the mixture was cooled to +10-15°С, then
(4.60 ml, 40 mmol) of t-BuOCl was added dropwise in the dark in argon atmosphere. The
reaction mixture was kept for 2 h at +10-15°С, then 22 h at room temperature. After the reaction
was completed, the solvent was removed at a reduced pressure, the residue dissolved in 80 ml of
ethyl acetate and treated with 90 ml of saturated aqueous Na2S2O3. The extract was dried with
CaCl2, solvent removed in vacuum, 5.44 g of light-yellow residue placed in a column with
coarse silica and eluted successively with hexane, hexane–ether 1:1, ether. From the hexane
eluate, (0.61 g, 12%) of (2-chloro-1-iodoethyl)trimethylsilane 5 was isolated as a liquid. From
ethereal-hexane eluate, yellow precipitate was obtained, which was crystallized from chloroform
to give (2.71 g, 52%) of N,N'-[1-(trimethylsilyl)ethane-1,2-diyl)bis(triflamide) 6 as a white
powder.
Products 7, 8 were isolated from the ethereal-hexane eluate in total yield (1.13 g, 13%).
Iodohydrin 9 is formed in trace amounts and was isolated from the hexane eluate, along with
product 5.

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4.2.2. Reaction of arenesulfonamides with vinyltrimethylsilane in the system t-BuOCl+NaI
(general procedure). To the solution of 10-13 mmol of arenesulfonamide and three-fold molar
excess of NaI 80 ml of CH3CN 15-19 mmol of trimethylvinylsilane was added, the mixture
cooled to +10-15°С, three-fold molar excess of t-BuOCl was added dropwise in the dark in
argon atmosphere, the reaction mixture kept for 2 h at +10-15°С, then 22 h at room temperature.
After completion of the reaction, the solvent was removed at a reduced pressure, the residue
dissolved in 80 ml of ethyl acetate and treated with 90 ml of saturated aqueous Na2S2O3. The
extract was dried with CaCl2, solvent removed in vacuum, the residue (3.5-4.5 g) was placed in a
column with coarse silica and eluted successively with hexane, hexane–эфир 1:1, ether. From
the hexane eluate, 6–19% of (2-chloro-1-iodoethyl)trimethylsilane was isolated as light liquid,
and from the ethereal-hexane eluate 71–91% of 1-arenesulfonyl-2-(trimethylsilyl)aziridine was
obtained as light-yellow oil (for X = H, Me, Cl) or white powder (X = NO2), which was
crystallized from chloroform.
4.2.3. Reaction of triflamide with dimethyldivinylsilane in the system t-BuOCl+NaI. To the
solution of (0.93 g, 6 mmol) of triflamide and (2.81 g, 19 mmol) of NaI in 60 ml of CH3CN (0.70
g, 6 mmol) of dimethyldivinylsilane was added, the mixture cooled to –30°С, (2.14 ml, 19
mmol) of t-BuOCl was added dropwise in the dark, the obtained mixture kept for 1.5 h at –30°С,
then 23 h at room temperature. After completion of the reaction, the solvent was removed under
reduced pressure, the residue dissolved in 70 ml of ethyl acetate and treated with 90 ml of
aqueous Na2S2O3. The extract was dried over CaCl2, solvent removed in vacuum, ~2.58 g of
light-yellow residue placed in a column with coarse silica and eluted successively with hexane,
mixture hexane–ether 1:1, ether. From hexane eluate, were obtained successively (0.10 g, 6%) of
(2-chloro-1-iodoethyl)dimethyl(vinyl)silane 13 as a liquid, then (7 mg, 3%) of dark-orange liquid
consisting of the mixture of diastereomers of bis(2-chloro-1-iodoethyl)dimethylsilane 14. From
ether-hexane eluate, 0.11 g of unreacted triflamide and (0.42 g, 20%) of N-(2-
{[dimethyl(vinyl)silyl]-2-iodoethyl}triflamide 12 (light-yellow oil) were obtained, and from the
ethereal eluate – light-yellow crystals which were purified by washing with chloroform to give
(0.64 g, 66%) of N-(3-(trifluoromethylsulfonyl)oxazolidin-5-yl)triflamide 11 as a white powder.
4.2.4. Reaction of benzenesulfonamide with dimethyldivinylsilane in the system t-
BuOCl+NaI. To the solution of (1.40 g, 9 mmol) of benzenesulfonamide and (4.02 g, 27 mmol)
of NaI in 70 ml of CH3CN (1.00 g, 9 mmol) of dimethylvinylsilane was added. The reaction was
carried out and treated as above. Light-yellow residue (3.29 g) was dissolved in chloroform, the
insoluble solid filtered and analyzed by NMR. The isolated powder was crystallized from
1
chloroform and dried to give 0.71 g of unreacted benzenesulfonamide (from Н NMR). The
yellow oily part soluble in chloroform (2.58 g) was placed in a column with coarse silica and

13
ACCEPTED MANUSCRIPT
eluted as in the previous synthesis. From the hexane eluate, were successively obtained (0.68 g,
28%) of compound 13 and (0.18 g, 5%) of diastereomeric mixture of compound 14. From ether-
hexane eluate, a mixture of crystalline and oily compounds was obtained, which was separated
by preparative TLC with eluent hexane–ether 2:1 to give (0.15 g, 13%) of 2-
[dimethyl(vinyl)silyl)-1-(phenylsulfonyl)aziridine 18a as a colorless oil and (0.48 g, 25%) of 2-
[(2-chloro-1-iodoethyl)dimethylsilyl]-1-(phenylsulfonyl)aziridine 19a as a light-yellow oil. The
crystalline residue was washed with ether and dried to afford (0.10 g, 4%) of analytically pure
3,5-diiodo-4,4-dimethyl-1-(phenylsulfonyl)-1,4-azasilinane 21a as a white powder. From the
ethereal eluate (0.19 g, 21%) of 2-{dimethyl[1-(phenylsulfonyl)aziridin-2-yl]silyl}-1-
(phenylsulfonyl)aziridine 20a was obtained as a colorless oily compound.
4.2.5. Reaction of tosylamide with dimethyldivinylsilane in the system t-BuOCl+NaI. To
the solution of (1.53 g, 9 mmol) of tosylamide and (4.02 g, 27 mmol) of NaI in 70 ml of CH3CN
(1.00 g, 9 mmol) of dimethyldivinylsilane was added. The reaction was carried out and treated as
above. The light-yellow residue (3.65 g) was placed in a column with coarse silica and eluted
successively with the same eluents as above. From the hexane eluate was isolated (0.65 g, 27%)
of compound 13, then (0.11 g, 3%) of the diastereomeric mixture of compound 14. From the
ether-hexane eluate, a mixture of crystals and light-yellow oil was obtained, which was washed
with ether to separate crystals from oil. The crystals were dried to afford (0.12 g, 4%) of
analytically pure 3,5-diiodo-4,4-dimethyl-1-tosyl-1,4-azasilinane 21b as a white powder. The oil
was purified on the column with fine silica using hexane and hexane–ether 1:1 as eluents. (0.13
g, 7%) of 2-[dimethyl(vinyl)silyl]-1-tosylaziridine 18b was isolated as a colorless oil. From the
ethereal eluate, the oily mixture of two products was obtained, which was separated by column
chromatography on coarse silica eluting with hexane and hexane–ether 1:1. (0.80 g, 29%) of 2-
[(2-chloro-1-iodoethyl)dimethylsilyl]-1-tosylaziridine 19b and (0.21 g, 15%) of 2-{dimethyl[1-
(tosylaziridin-2-yl)silyl]-1-tosylaziridine 20b as colorless oils were obtained.
4.2.6. Reaction of p-chlorobenzenesulfonamide with dimethyldivinylsilane in the system t-
BuOCl+NaI. To the solution of (3.42 g, 18 mmol) of p-chlorobenzenesulfonamide and (8.04 g,
54 mmol) of NaI in 70 ml of CH3CN (2.00 g, 18 mmol) of dimethyldivinylsilane was added. The
reaction was carried out and treated as above. The light-yellow residue (6.83 g) was placed in a
column with coarse silica and eluted successively with the same eluents as above. From the
hexane eluate was isolated (0.70 g, 14%) of compound 13, then (0.11 g, 3%) of the
diastereomeric mixture of compound 14. Then, from the hexane solution white crystals
precipitated (0.30 g, 4%), which proved to be 1-(4-chlorophenylsulfonyl)-3,5-diiodo-4,4-
dimethyl-1,4-azasilinane 21c. From ether-hexane eluate, light-yellow oil was obtained, which
was purified on a column with coarse silica eluting with hexane and hexane–ether 1:1 to afford

14
ACCEPTED MANUSCRIPT
3.84 g (55%) of 2-[(2-chloro-1-iodoethyl)dimethylsilyl]-1-(4-chlorophenylsulfonyl)aziridine 19c
as a colorless oil. From the ethereal eluate, yellow oil was obtained, which was additionally
purified by column chromatography on coarse silica using hexane and hexane–ether 1:1 as
eluents. (0.41 g, 11%) of 1-(4-chlorophenylsulfonyl)-2-{[1-(4-chlorophenylsulfonyl)aziridin-2-
yl]dimethylsilyl}aziridine 20c as a colorless oil.
4.2.7. Reaction of p-nitrobenzenesulfonamide with dimethyldivinylsilane in the system t-
BuOCl+NaI. To the solution of (1.80 g, 9 mmol) of p-nitrobenzenesulfonamide and (4.02 g, 27
mmol) of NaI in 70 ml of CH3CN (1.00 g, 9 mmol) of dimethyldivinylsilane was added. The
reaction was carried out and treated as above. The light-yellow residue (4.46 g) was placed in a
column with coarse silica and eluted successively with the same eluents as above. From the
hexane eluate was isolated (0.55 g, 23%) of compound 13, then (0.12 g, 3%) of the
diastereomeric mixture of compound 14. Then, from the hexane eluate, white crystals of 3,5-
diiodo-4,4-dimethyl-1-(4-nitrophenylsulfonyl)-1,4-azasilinane 21d (0.07 g, 2.4%) precipitated.
From ether-hexane eluate, light-yellow powder was obtained, which was purified on fine silica
using hexane and hexane–ether 1:1 as eluents. (0.87 g, 54%) of 2-[dimethyl(vinyl)silyl]-1-(4-
nitrophenylsulfonyl)aziridine 18d was isolated as a white powder. From the ethereal eluate,
yellow powder was obtained and further purified on a column with coarse silica eluted with
hexane and hexane–ether 1:1 to afford (0.29 g, 12%) of 2-[(2-chloro-1-iodoethyl)dimethylsilyl]-
1-(4-nitrophenylsulfonyl)aziridine 19d as a white powder.
4.2.8. Reaction of p-nitrobenzenesulfonamide with (2-chloro-1-iodoethyl)dimethyl(vinyl)-
silane 10 in the system t-BuOCl+NaI. To the solution of (0.51 g, 2.6 mmol) of p-nitrobenzene-
sulfonamide and (1.15 g, 7.6 mmol) of NaI in 50 ml of CH3CN (0.70 g, 2.6 mmol) of (2-chloro-
1-iodoethyl)dimethyl(vinyl)silane 13 was added, the mixture cooled to –30°С, then (0.87 ml, 7.6
mmol) of t-BuOCl was added dropwise in the dark in argon atmosphere. The reaction mixture
was kept for 1.5 h at –30°С, then 23 h at room temperature. After completion of the reaction, the
solvent was removed at a reduced pressure, the residue dissolved in 50 ml of ethyl acetate and
treated with 60 ml of aqueous Na2S2O3. The extract was dried over CaCl2, solvent removed in
vacuum, the light-yellow residue (0.97 g) analyzed by NMR spectroscopy, which showed the
presence of products 14 (37%), 19d (16%) and 10% of unreacted 13 (the yields are given based
on the 1H NMR spectroscopy data).
4.2.9. Reaction of p-nitrobenzenesulfonamide with 2-[dimethyl(vinyl)silyl)-1-(4-nitro-
phenylsulfonyl)aziridine 15d in the system t-BuOCl+NaI. To the solution of (0.26 g, 1.3 mmol)
of p-nitrobenzenesulfonamide and (0.58 g, 3.8 mmol) of NaI in 50 ml of CH3CN (0.40 g, 1.3
mmol) of 2-[dimethyl(vinyl)silyl]-1-(4-nitrophenylsulfonyl)aziridine 18d was added, the mixture
cooled to –30°С and (0.44 ml, 3.8 mmol) of t-BuOCl was added dropwise in the dark in argon

15
ACCEPTED MANUSCRIPT
atmosphere. The reaction mixture was kept for 1.5 h at –30°С, then 23 h at room temperature.
After completion of the reaction, the solvent was removed at a reduced pressure, the residue
dissolved in 50 ml of ethyl acetate and treated with 60 ml of aqueous Na2S2O3. The extract was
dried over CaCl2, solvent removed in vacuum, 0.55 g of light-yellow residue analyzed by NMR
spectroscopy, which showed the presence of products 19d (80%) and 2-{dimethyl[1-(4-
nitrophenylsulfonyl)aziridin-2-yl]silyl}-1-(4-nitrophenylsulfonyl)aziridine 20d (20%) (the yields
are given based on the 1H NMR spectroscopy data).
4.2.10. (2-Сhloro-1-iodoethyl)trimethylsilane, 5. Liquid, yields see in Table 1 in the main
text. IR (KBr) 2956, 2104, 1945, 1516, 1420, 1295, 1254, 1137, 1032, 845, 760, 694, 607, 539,
1
497 cm–1. H NMR (400 MHz, CDCl3, δ, ppm) 3.92 (dd, CHH, J 11.8, 5.9 Hz, 1H), 3.88 (dd,
13
CHH, J 11.8, 9.2 Hz, 1H), 3.38 (dd, CH, J 9.2, 5.9 Hz, 1H), 0.22 (s, CH3, 9H). C NMR (100
MHz, CDCl3, δ, ppm) 48.7 (CH2Cl), 20.1 (CHI), -1.5 (CH3). 29Si NMR (79.5 MHz, CDCl3 δ,
ppm) 7.21. Anal. calcd for C5H12ClISi: C, 22.87; H, 4.61; I, 48.33; Si, 10.70. Found: C, 22.61;
H, 4.51; I, 48.12; Si, 10.51.
4.2.11. N,N'-(1-(Trimethylsilyl)ethane-1,2-diyl)bis(1,1,1-trifluoromethanesulfonamide), 6.
White solid. Mp 125 °C. 52% yield. IR (KBr) 3384, 3298, 2971, 1453, 1444, 1366, 1231, 1195,
1
1145, 1059, 960, 907, 853, 760, 727, 609, 572, 487, 441 cm–1. H NMR (400 MHz, CD3CN δ,
ppm) 6.72 (br.tr, NHCH2, J 5.62 Hz), 6.56 (br.d, NHCH, J 9.1 Hz), 3.49 (dtr, CH, J 14.1, 3.7 Hz,
1H), 3.32 (dtr, CHH, J 14.1, 9.1 Hz, 1H), 3.20 (dtr, CHH, J 9.1, 3.7 Hz, 2H), 0.16 (s, CH3, 9H).
13C NMR (100 MHz, CD3CN, δ, ppm) 120.8 (q, J 320.9 Hz, CF3), 120.7 (q, J 320.0 Hz, CF3),
19
48.3 (CH2), 47.1 (CH), –3.1 (CH3). F NMR (376 MHz, CD3CN, δ, ppm) –77.9, –78.1. 29Si
NMR (79.5 MHz, CDCl3, δ, ppm) 5.34. Anal. calcd for C7H14F6N2O4S2Si: C, 21.21; H, 3.56; N,
7.07; S, 16.18; F, 28.76; Si, 7.09. Found: C, 21.20; H, 3.51; N, 7.01; S, 16.15; F, 28.43; Si, 7.02.
1
4.2.12. N-[2-Iodo-2-(trimethylsilyl)ethyl]triflamide, 7. Yellow oil. H NMR (400 MHz,
CD3CN, δ, ppm) 5.49 (br. tr, NH, J ~6 Hz), 3.76-3.61 (m, CHBN in 7 and CHN in 8), 3.50-3.35
(m, CHAN in 7 and CHBCl in 8), 3.21 (dd, CHI, J 11.2, 3.2 Hz, 1H), 0.21 (s, CH3, 9H). 13C NMR
(100 MHz, CD3CN, δ, ppm) 119.5 (q, J 321.0 Hz, CF3), 48.1 (CH2N), 19.6 (CHI), –2.4 (CH3).
19F NMR (376 MHz, CD3CN, δ, ppm) –77.19. 29Si NMR (79.5 MHz, CDCl3, δ, ppm) 6.56.
1
4.2.13. N-[2-Chloro-1-(trimethylsilyl)ethyl]triflamide, 8. Yellow oil. H NMR (400 MHz,
CD3CN, δ, ppm) 5.46 (br. d, NH, J 5.9 Hz), 3.80-3.68 (m, CHN, 1H), 3.43 (dd, CHBCl, J 11.3,
3.0 Hz, 1H), 3.40-3.35 (m, CHACl, 1H), 0.19 (s, CH3, 9H); 13C NMR (100 MHz, CD3CN, δ,
ppm) 119.5 (q, J 321.0 Hz, CF3), 50.4 (CHN), 47.7 (CH2Cl), –3.8 (CH3). 19F NMR (376 MHz,
CD3CN, δ, ppm) –77.24. 29Si NMR (79.5 MHz, CDCl3, δ, ppm) 5.11.
1
4.2.14. 2-Iodo-2-(trimethylsilyl)ethanol, 9. Liquid. H NMR (400 MHz, CDCl3, δ, ppm)
3.67 (dd, CHH, J 10.2, 7.3 Hz, 1H), 3.61 (dd, CHH, J 10.0, 5.6 Hz, 1H), 3.22 (dd, CH, J 7.3, 5.6

16
ACCEPTED MANUSCRIPT
13
Hz, 1H), 0.17 (s, CH3, 9H). C NMR (100 MHz, CDCl3, δ, ppm) 73.1 (CH2OH), 20.0 (CHI), -
1.4 (CH3); 29Si NMR (79.5 MHz, CDCl3, δ, ppm) 6.01.
4.2.15. 1-(Phenylsulfonyl)-2-(trimethylsilyl)aziridine, 10a. Light-yellow oil. 71% yield. IR
(KBr): 2957, 1448, 1321, 1252, 1207, 1162, 1091, 954, 904, 846, 738, 690, 662, 595, 542 cm–1.
1H NMR (400 MHz, CDCl3, δ, ppm) 7.92 (d, o-CH, J 7.8 Hz, 2H), 7.61 (tr, p-CH, J 7.8 Hz, 1H),
7.52 (tr, m-CH, J 7.8 Hz, 2H), 2.69 (d, CHHN, J 8.7 Hz, 1H), 2.07 (d, CHHN, J 5.8 Hz, 2H),
13
2.07 (dd, CHN, J 8.7, 5.8 Hz, 2H), -0.11 (s, CH3, 9H). C NMR (100 MHz, CDCl3, δ, ppm)
138.0 (Ci), 133.3 (Cp), 128.8 (Co), 127.8 (Cm), 30.2 (CH2N), 29.9 (CHN), -3.9 (CH3). 29Si NMR
(79.5 MHz, CDCl3, δ, ppm) 1.44. Anal. calcd for C11H17NO2SSi: C, 51.73; H, 6.71; N, 5.48; S,
12.55; Si, 11.00. Found: C, 51.70; H, 6.56; N, 5.45; S, 12.49; Si, 10.94.
4.2.16. 1-Tosyl-2-(trimethylsilyl)aziridine, 10b. Light-yellow oil, 86% yield. IR (KBr)
2958, 2900, 1921, 1598, 1494, 1451, 1408, 1323, 1299, 1253, 1208, 1158, 1094, 954, 905, 847,
815, 758, 700, 656, 557, 494 cm–1. 1H NMR (400 MHz, CDCl3, δ, ppm) 7.79 (d, o-CH, J 8.2 Hz,
2H), 7.30 (d, m-CH, J 8.2 Hz, 2H), 2.64 (d, CHHN, J 8.7 Hz, 1H), 2.41 (s, CH3Ph, 3H), 2.04 (d,
13
CHHN, J 5.8 Hz, 1H), 1.87 (dd, CHN, J 8.7, 5.8 Hz, 1H), -0.11 (s, CH3, 3H). C NMR (100
MHz, CDCl3, δ, ppm) 143.9 (Cp), 134.6 (Ci), 129.1 (Cm), 127.6 (Co), 29.9 (CHN), 29.4 (CH2N),
21.0 (CH3Ph), -4.2 (CH3); 29Si NMR (79.5 MHz, CDCl3, δ, ppm) 1.49. Anal. calcd for
C12H19NO2SSi: C, 53.49; H, 7.11; N, 5.20; S, 11.90; Si, 10.42. Found C, 53.45; H, 7.08; N, 5.20;
S, 11.84; Si, 10.40.
4.2.17. 1-(4-Chlorophenylsulfonyl)-2-(trimethylsilyl)aziridine, 10c. Light-yellow oil. 84%
yield. IR (KBr) 3092, 2958, 1582, 1475, 1396, 1327, 1253, 1208, 1163, 1091, 1014, 954, 905,
1
846, 761, 707, 673, 626, 544, 482 cm–1. H NMR (400 MHz, CDCl3, δ, ppm) 7.85 (d, o-CH, J
8.4 Hz, 2H), 7.49 (d, m-CH, J 8.4 Hz, 2H), 2.66 (d, CHHN, J 8.6 Hz, 1H), 2.06 (d, CHHN, J 5.8
Hz, 1H), 1.93 (dd, CHN, J 8.6, 5.8 Hz, 1H), -0.06 (s, CH3, 9H). 13C NMR (100 MHz, CDCl3, δ,
29
ppm) 139.6 (Cp), 136.5 (Ci), 129.2 (Co), 128.9 (Cm), 30.4 (CH2N), 30.0 (CHN), -4.0 (CH3). Si
NMR (79.5 MHz, CDCl3, δ, ppm) 1.71. Anal. calcd for C11H16ClNO2SSi: C, 45.58; H, 5.56; N,
4.83; S, 11.06; Si, 9.69; Cl, 12.23. Found: C, 45.37; H, 5.41; N, 4.46; S, 11.03; Si, 9.57; Cl,
12.19.
4.2.18. 1-(4-Nitrophenylsulfonyl)-2-(trimethylsilyl)aziridine, 10d. White solid. Mp 128
(±2) °C. 91% yield. IR (KBr) 3102, 2957, 1606, 1527, 1404, 1305, 1249, 1210, 1170, 1090, 955,
1
896, 845, 752, 687, 613, 539, 459 cm–1. H NMR (400 MHz, CDCl3, δ, ppm) 8.39 (d, m-CH, J
8.7 Hz, 2H), 8.15 (d, o-CH, J 8.7 Hz, 2H), 2.76 (d, CHHN, J 8.5 Hz, 1H), 2.15 (d, CHHN, J 6.0
Hz, 1H), 2.09 (dd, CHN, J 8.5, 6.0 Hz, 1H), -0.04 (s, CH3, 3H). 13C NMR (100 MHz, CDCl3, δ,
ppm) 150.5 (Ci), 144.1 (Cp), 129.3 (Co), 124.1 (Cm), 31.2 (CH2N), 31.0 (CHN), -3.8 (CH3). 29Si

17
ACCEPTED MANUSCRIPT
NMR (79.5 MHz, CDCl3, δ, ppm) 1.90. Anal. calcd for C11H16N2O4SSi: C, 43.98; H, 5.37; N,
9.33; S, 10.67; Si, 9.35; found: C, 43.95; H, 5.30; N, 9.31; S, 10.60; Si, 9.29.
4.2.19. N-[3-(Trifluoromethylsulfonyl)oxazolidin-5-yl]triflamide, 11. White solid. Mp 128
(±2) °C. 66% yield. IR (KBr) 3559, 3303, 2901, 2262, 1445, 1377, 1198, 1075, 1005, 873, 827,
607 cm–1. 1H NMR (400 MHz, CD3CN, δ, ppm) 7.87 (br. s, NH), 3.63 (m, NCH2O and NCHO,
3H), 3.93 (dd, ClCHH, J 11.6, 5.0 Hz, 2H), 3.73 (m, ICH, 2H), 0.48 (s, CH3, 6H); 13C NMR (100
MHz, CDCl3, δ, ppm) 135.3 (=CH), 134.6 (=CH2), 48.7 (CH2Cl), 18.7 (CHI), -3.0 (CH3), -3.4
(CH3). 19F NMR (376 MHz, CDCl3, δ, ppm) –78.30, –78.57. Anal. calcd for C5H6F6N2O5S2: C,
17.05; H, 1.72; N 7.95; S 18.21; F 32.36. Found: C, 17.00; H, 1.68; N, 7.91; S, 18.09; F, 32.12.
4.2.20. N-{2-[Dimethyl(vinyl)silyl]-2-iodoethyl}triflamide, 12. Light-yellow oil. 20% yield.
IR (KBr) 3574, 3319, 1636, 1552, 1443, 1397, 1318, 1229, 1197, 1141, 1065, 839, 602 cm–1. 1H
NMR (400 MHz, CDCl3, δ, ppm) 6.56 (dd, =CH, J 15.6, 9.0 Hz, 1H), 5.98 (br. s, NH), 4.82 (dd,
=CHH, J 9.0, 2.0 Hz, 1H), 4.74 (dd, =CHH, J 15.6, 2.0 Hz, 1H), 4.02 (d, CH2, J 8.0 Hz, 2H),
3.51 (tr, CH, J 8.0 Hz, 1H), 0.41 (s, CH3, 3H), 0.39 (s, CH3, 3H). 13C NMR (100 MHz, CDCl3, δ,
ppm) 129.3 (=CH), 119.80 (q, J 326.6 Hz, CF3), 100.7 (=CH2), 49.5 (CH2NH), 11.7 (CHI), -1.2
(CH3), -1.6 (CH3). 19F NMR (376 MHz, CDCl3, δ, ppm) –78.9; 29Si NMR (79.5 MHz, CDCl3, δ,
ppm) 13.6. Anal. calcd for C7H13F3INO2SSi: C, 21.71; H, 3.38; N, 3.62; S, 8.28; Si, 7.25; F,
14.72; I, 32.77. Found: C, 21.66; H, 3.32; N, 3.60; S, 8.15; Si, 7.19; F, 14.59; I, 32.55.
4.2.21. (2-Chloro-1-iodoethyl)dimethyl(vinyl)silane, 13. Liquid. Yields see in Scheme 7
and Table 2 in the main text. IR (KBr) 3051, 2956, 1406, 1295, 1253, 1008, 958, 819, 781, 702,
602, 534 cm–1. 1H NMR (400 MHz, CDCl3, δ, ppm) 6.24 (dd, =CHH, J 19.5, 14.8 Hz, 1H), 6.11
(dd, =CHH, J 14.8, 3.9 Hz, 1H), 5.81 (dd, =CH, J 19.5, 3.9 Hz, 1H), 3.93 (dd, CHH, J 11.9, 5.4
Hz, 1H), 3.83 (dd, =CHH, J 11.9, 9.6 Hz, 1H), 3.38 (dd, =CH, J 9.6, 5.4 Hz, 1H), 0.31 (s, CH3,
6H). 13C NMR (100 MHz, CDCl3, δ, ppm) 135.3 (=CH), 134.6 (=CH2), 48.7 (CH2Cl), 18.7
29
(CHI), -3.0 (CH3), -3.4 (CH3). Si NMR (79.5 MHz, CDCl3, δ, ppm) -1.42. Anal. calcd for
C6H12ClISi: C, 26.24; H, 4.40; I, 46.21; Si, 10.23. Found: C, 26.19; H, 4.20; I, 45.87; Si, 10.09.
4.2.22. Bis(2-chloro-1-iodoethyl)dimethylsilane, 14. Liquid. Yields see in Scheme 7 and
Table 2 in the main text. IR (KBr) 2957, 2929, 1391, 1295, 1256, 1193, 1137, 1030, 922, 816,
789, 719, 594, 494 cm–1. 1H NMR (400 MHz, CDCl3, δ, ppm) 3.99 (dd, ClCHH, J 11.6, 8.6 Hz,
2H), 3.93 (dd, ClCHH, J 11.6, 5.0 Hz, 2H), 3.78-3.69 (m, ICH, 2H), 0.49 (s, CH3, 6H, major
R,S-diastereomer), 0.462 and 0.457 (s, CH3, 6H, minor (R,R+S,S)-diastereomer). 13C NMR (100
MHz, CDCl3, δ, ppm), major diastereomer: 47.6 (CH2Cl), 16.7 (CHI), -3.3 (CH3); minor
diastereomer: δ47.9 (CH2Cl), 17.0 (CHI), -2.1 and -3.8 (CH3). 29Si NMR (79.5 MHz, CDCl3, δ,
ppm) 9.59. Anal. calcd for C6H12Cl2I2Si: C, 16.49; H, 2.77; I 58.09; Si 6.43. Found: C, 16.15; H,
2.36; I, 56.90; Si, 6.40.

18
ACCEPTED MANUSCRIPT
4.2.23. 2-[Dimethyl(vinyl)silyl]-1-(phenylsulfonyl)aziridine, 18a. Colorless oil, 13% yield.
IR (KBr) 1714, 1449, 1407, 1321, 1253, 1211, 1162, 1092, 1010, 957, 905, 836, 756, 664, 597
1
cm–1. H NMR (400 MHz, CDCl3, δ, ppm) 7.95 (d, o-CH, J 7.8 Hz, 2H), 7.64 (tr, p-CH, J 7.8
Hz, 1H), 7.54 (tr, m-CH, J 7.8 Hz, 2H), 5.96 (dd, =CHH, J 14.6, 4.6 Hz, 1H), 5.90 (dd, =CH, J
18.2, 14.6 Hz, 1H), 5.67 (dd, =CHH, J 18.2, 4.6 Hz, 1H), 2.72 (d, CHHN, J 8.4 Hz, 1H), 2.10 (d,
CHHN, J 5.7 Hz, 1H), 1.98 (dd, CHN, J 8.4, 5.7 Hz, 1H), -0.02 (s, CH3, 3H), -0.03 (s, CH3, 3H).
13C NMR (100 MHz, CDCl3, δ, ppm) 134.5 (Ci), 134.4 (Cp), 134.3 (=CH), 133.4 (=CH2), 128.9
29
(Co), 128.1 (Cm), 30.4 (CHNH), 29.4 (CH2N), -5.5 (CH3), -5.7 (CH3). Si NMR (79.5 MHz,
CDCl3, δ, ppm) -6.34. Anal. calcd for C12H17NO2SSi: C, 53.90; H, 6.41; N, 5.24; S, 11.99; Si,
10.50. Found: C, 53.73; H, 6.35; N, 5.20; S, 11.86; Si, 10.32.
4.2.24. 2-(Dimethyl(vinyl)silyl)-1-tosylaziridine, 18b. Colorless oil. 7% yield. IR (KBr)
2961, 1597, 1406, 1325, 1254, 1205, 1160, 1091, 1014, 955, 905, 835, 811, 703 cm–1. 1H NMR
(400 MHz, CDCl3, δ, ppm) 7.81 (d, o-CH, J 8.2 Hz, 2H), 7.33 (d, m-CH, J 8.2 Hz, 2H), 5.96 (dd,
=CHH, J 14.7, 6.2 Hz, 1H), 5.92 (dd, =CH, J 18.0, 14.4 Hz, 1H), 5.67 (dd, =CHH, J 18.0, 6.2
Hz, 1H), 2.67 (d, CHHN, J 8.5 Hz, 1H), 2.45 (s, CH3Ph, 3H), 2.07 (d, CHHN, J 5.8 Hz, 1H),
1.95 (dd, CHN, J 8.4, 5.8 Hz, 1H), -0.01 (s, CH3, 3H), -0.02 (s, CH3, 3H). 13C NMR (100 MHz,
CDCl3, δ, ppm) 144.3 (Cp), 135.1 (=CH), 134.6 (Ci), 134.1 (=CH2), 129.5 (Cm), 128.1 (Co), 30.3
(CHN), 29.1 (CH2N), 21.5 (CH3Ph), -5.4 (CH3), -5.6 (CH3). 29Si NMR (79.5 MHz, CDCl3, δ,
ppm) -6.56. Anal. calcd for C13H19NO2SSi: C, 55.48; H, 6.80; N, 4.98; S, 11.39; Si, 9.98. Found:
C, 55.41; H, 6.77; N, 4.92; S, 11.31; Si, 9.90.
4.2.25. 2-[Dimethyl(vinyl)silyl]-1-[(4-chlorophenyl)sulfonyl]aziridine, 18c. From the
fraction with 19c as the major component. Yield (from NMR) 45%. 1H NMR (400 MHz, CDCl3,
δ, ppm) 7.91–7.85 (m, m-CH, 2H), 7.56–7.47 (m, o-CH, 2H), 6.0–5.84 (m, =CH2, 2H), 5.67 (dd,
CH=, J 19.1, 5.0 Hz, 1H), 2.02–1.95 (m, CHN, 1H), 0.05 (s, CH3, 3H), –0.01 (s, CH3, 3H); the
CH2 signals of the aziridine ring overlap with the corresponding signals of 19c.
4.2.26. 2-[Dimethyl(vinyl)silyl]-1-[(4-nitrophenyl)sulfonyl]aziridine, 18d. White solid. Mp
96 °C. 54% yield. IR (KBr) 3286, 3107, 2964, 1939, 1605, 1532, 1405, 1346, 1309, 1254, 1206,
1165, 1093, 1012, 957 cm–1. 1H NMR (400 MHz, CDCl3, δ, ppm) 8.39 (d, m-CH, J 8.8 Hz, 2H),
8.13 (d, o-CH, J 8.8 Hz, 2H), 5.98 (dd, =CHH, J 14.6, 4.5 Hz, 1H), 5.91 (dd, =CH, J 19.3, 14.6
Hz, 1H), 5.70 (dd, =CHH, J 19.3, 4.5 Hz, 1H), 2.77 (dd, CHHN, J 8.2, 0.67 Hz, 1H), 2.16 (d,
CHHN, J 5.9, 0.7 Hz, 1H), 2.12 (dd, CHN, J 8.1, 5.9 Hz, 1H), 0.03 (s, CH3, 3H), 0.02 (s, CH3,
13
3H). C NMR (100 MHz, CDCl3, δ, ppm) 150.5 (Cp), 144.0 (Ci), 134.4 (=CH), 134.0 (=CH2),
129.3 (Co), 124.1 (Cm), 31.1 (CHN), 30.2 (CH2N), -5.6 and -5.7 (CH3); 29Si NMR (79.5 MHz,
CDCl3, δ, ppm) -6.35. Anal. calcd for C12H16N2O4SSi: C, 46.13; H, 5.16; N, 8.97; S, 10.26; Si,
8.99. Found: C, 46.10; H, 5.12; N, 8.94; S, 10.21; Si, 8.95.

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4.2.27. 2-[(2-Chloro-1-iodoethyl)dimethylsilyl]-1-(phenylsulfonyl)aziridine, 19a. Light-
yellow oil. 25% yield. IR (KBr) 2958, 1705, 1447, 1321, 1255, 1162, 1090, 903, 818, 737 cm–1.
1H NMR (400 MHz, CDCl3, δ, ppm) 7.95 (d, o-CH, J 7.8 Hz, 2H), 7.67 (tr, p-CH, J 7.8 Hz, 1H),
7.57 (tr, m-CH, J 7.8 Hz, 2H), 3.85 (d, CH2Cl, J 7.2 Hz, 2H), 3.36 (trd, CHI, J 7.2, 5.5 Hz, 1H),
2.74 (d, CHN, J 8.4 Hz, 1H), 2.19-2.13 (m, CH2N, 2H), 0.16 (s, CH3, 3H), 0.07 (s, CH3, 3H). 13C
NMR (100 MHz, CDCl3, δ, ppm) 133.8 (Ci), 132.9 (Cp), 129.1 (Co), 128.2 (Cm), 47.66 (CH2Cl),
30.88 (CH2N), 28.4 (CHN), 14.8 (CHI), -4.3 and -5.9 (CH3). 29Si NMR (79.5 MHz, CDCl3, δ,
ppm) 5.87. Anal. calcd for C12H17ClINO2SSi: C, 33.54; H, 3.99; N, 3.26; I, 29.53; S, 7.46; Si,
6.53. Found: C, 33.24; H, 3.98; N, 3.11; I, 28.87; S, 7.30; Si, 6.14.
1
Minor diastereomer: H NMR (400 MHz, CDCl3, δ, ppm) 3.87 (d, CH2Cl, J 7.3, 1.5 Hz,
2H), 3.42-3.38 (m, CHI, 1H), 2.20 (dd, CH2N, J 8.4, 5.7 Hz, 2H), 0.17 (s, CH3, 3H), 0.04 (s,
CH3, 3H). 13C NMR (100 MHz, CDCl3, δ, ppm) 47.74 (CH2Cl), 30.80 (CH2N), 28.7 (CHN),
15.0 (CHI), -5.28 and -5.34 (CH3). 29Si NMR (79.5 MHz, CDCl3, δ, ppm) 5.98.
4.2.28. 2-[(2-Chloro-1-iodoethyl)dimethylsilyl]-1-tosylaziridine, 19b. Colorless oil. 29%
yield. IR (KBr): 3284, 2958, 1593, 1406, 1326, 1160, 1088, 906, 815 cm–1. 1H NMR (400 MHz,
CDCl3, δ, ppm) 7.82 (d, o-CH, J 8.1 Hz, 2H), 7.35 (d, m-CH, J 8.1 Hz, 2H), 3.87-3.76 (m,
CH2Cl, 2H), 3.38-3.32 (m, CHI, 1H), 2.69 (d, CHN, J 8.5 Hz, 1H), 2.46 (s, CH3Ph, 3H), 2.15-
2.10 (m, CH2N, 2H), 0.16 (s, CH3, 3H), 0.09 (s, CH3, 3H). 13C NMR (100 MHz, CDCl3, δ, ppm)
144.8 (Cp), 143.6 (Ci), 129.7 (Cm), 128.2 (Co), 47.72 (CH2Cl), 30.65 (CH2N), 28.05 (CHN),
21.59 (CH3Ph), 15.16 (CHI), -4.4 and -5.8 (CH3). 29Si NMR (79.5, CDCl3, δ, ppm) 5.61. Anal.
calcd for C13H19ClINO2SSi: C, 35.18; H, 4.32; N, 3.16; I, 28.59; S, 7.23; Si, 6.33. Found: C,
35.15; H, 4.31; N 3.13; I, 28.33; S, 7.03; Si, 6.28.
1
Minor diastereomer, H NMR (400 MHz, CDCl3, δ, ppm) 2.44 (s, CH3Ph, 3H), 2.18-2.15 (m,
13
CH2N, 2H), 0.17 (s, CH3, 3H), 0.06 (s, CH3, 3H). C NMR (100 MHz, CDCl3, δ, ppm) 47.81
(CH2Cl), 30.62 (CH2N), 28.46 (CHN), 21.46 (CH3Ph), 15.28 (CHI), -5.1 and -5.5 (CH3). 29Si
NMR (79.5 MHz, CDCl3, δ, ppm) 5.69.
4.2.29. 2-[(2-Chloro-1-iodoethyl)dimethylsilyl]-1-[(4-chlorophenyl)sulfonyl]aziridine, 19c.
Colorless oil. 55% yield. IR (KBr) 3290, 3090, 2962, 2255, 1581, 1475, 1397, 1327, 1257, 1206,
1
1162, 1089, 904, 798, 674 cm–1. H NMR (400 MHz, CDCl3, δ, ppm) 7.88 (d, o-CH, J 8.6 Hz,
2H), 7.54 (d, m-CH, J 8.6 Hz, 2H), 3.88 (dd, CHHCl, J 7.1, 3.7 Hz, 1H), 3.38 (q, CHHCl, J 7.1
Hz, 1H), 2.71 (dd, CHI, J 8.5, 1.5 Hz, 1H), 2.22 (ddd, CHHN, J 10.9, 5.4, 5.8 Hz, 1H), 2.15 (dd,
CHHN, J 5.8, 1.5 Hz 1H), 0.17 (s, CH3, 3H), 0.11 (s, CH3, 3H). 13C NMR (100 MHz, CDCl3, δ,
ppm) 140.36 (Cp), 136.08 (Ci), 129.6 (Co), 129.4 (Cm), 47.68 (CH2Cl), 31.15 (CH2N), 28.56
(CHN), 14.64 (CHI), -4.3 and -6.0 (CH3). 29Si NMR (79.5 MHz, CDCl3, δ, ppm) 5.71. Anal.

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calcd for C12H16Cl2INO2SSi: C, 31.05; H, 3.47; N, 3.02; I, 27.34; S, 6.91; Si, 6.05. Found: C,
31.00; H, 3.45; N, 3.01; I, 27.30; S, 6.86; Si, 6.02.
1
Minor diastereomer: H NMR (400 MHz, CDCl3, δ, ppm) 0.17 (s, CH3, 3H), 0.06 (s, CH3, 3H).
13C NMR (100 MHz, CDCl3, δ, ppm) 140.34 (Cp), 136.15 (Ci), 47.60 (CH2Cl), 31.04 (CH2N),
28.95 (CHN), 14.75 (CHI), -5.24 and -5.32 (CH3); 29Si NMR (79.5 MHz, CDCl3, δ, ppm) 5.83.
4.2.30. 2-([(2-Chloro-1-iodoethyl)dimethylsilyl]-1-[(4-nitrophenyl)sulfonyl]aziridine, 19d.
White solid. Mp 97 °C. 12% yield. IR (KBr) 3106, 2958, 1608, 1532, 1346, 1309, 1164, 1091,
1
904, 849, 796, 747 cm–1. H NMR (400 MHz, CDCl3, δ, ppm) 8.42 (d, m-CH, J 8.6 Hz, 2H),
8.17 (d, o-CH, J 8.6 Hz, 2H), 3.93 (dd, CHHCl, J 11.6, 7.0 Hz, 1H), 3.89 (dd, CHHCl, J 11.6,
5.5 Hz, 1H), 3.93 (dd, CHI, J 7.0, 5.5 Hz, 1H), 2.79 (dd, CHN, J 8.5, 1.5 Hz, 1H), 2.37 (ddd,
CHHN, J 8.5, 5.8, 1.5 Hz, 1H), 2.12 (dd, CHHN, J 5.8, 1.5 Hz 1H), 0.19 (s, CH3, 3H), 0.15 (s,
13
CH3, 3H). C NMR (100 MHz, CDCl3, δ, ppm) 150.7 (Cp), 143.5 (Ci), 129.5 (Co), 124.3 (Cm),
47.47 (CH2Cl), 31.84 (CH2N), 29.28 (CHN), 14.05 (CHI), -4.1 and -6.0 (CH3). 29Si NMR (79.5
MHz, CDCl3, δ, ppm) 5.88. Anal. calcd for C12H16ClIN2O4SSi: C, 30.36; H, 3.40; Cl, 7.47; I,
26.73; N, 5.90; S, 6.75; Si, 5.92. Found: C, 30.33; H, 3.39; N 5.88; I, 26.68; S, 6.68; Si, 5.89.
Minor diastereomer: 1H NMR (400 MHz, CDCl3, δ, ppm) 0.20 (s, CH3, 3H), 0.13 (s, CH3,
13
3H). C NMR (100 MHz, CDCl3, δ, ppm) 47.53 (CH2Cl), 31.66 (CH2N), 29.67 (CHN), 14.16
(CHI), -5.0 and -5.4 (CH3). 29Si NMR (79.5 MHz, CDCl3, δ, ppm) 6.03.
4.2.31. Dimethylbis[1-(phenylsulfonyl)aziridin-2-yl]silane, 20a. Colorless oil. 21% yield.
IR (KBr) 2961, 2904, 2256, 1589, 1447, 1320, 1258, 1206, 1163, 1083, 1066, 905, 841, 798,
1
737, 589 cm–1. H NMR (400 MHz, CDCl3, δ, ppm) 7.92 (d, o-CH, J 7.8 Hz, 2H), 7.63 (tr, p-
CH, J 7.8 Hz, 1H), 7.54 (tr, m-CH, J 7.8 Hz, 2H), 2.62 (dd, CHBN, J 8.6, 2.8 Hz, 1H), 2.06 (dd,
CHAN, J 5.7, 2.8 Hz, 1H), 1.90 (dtr, CHN, J 8.6, 5.7 Hz, 1H), -0.07 and -0.09 (s, CH3, 6H, major
(R,R+S,S)-diastereomer), -0.05 (s, CH3, 6H, minor R,S-diastereomer). 13C NMR (100 MHz,
CDCl3, δ, ppm) 138.0 (Ci), 133.5 (Cp), 129.0 (Co), 128.0 (Cm), 30.2 (CH2N), 29.4 (CHNH), -1.37
and 1.42 [CH3, major (R,R+S,S)-diastereomer], -2.1 (CH3, minor R,S-diastereomer). 29Si NMR
(79.5 MHz, CDCl3, δ, ppm) 3.66.
4.2.32. Dimethylbis(1-tosylaziridin-2-yl)silane, 20b. Colorless oil. 15% yield. IR (KBr)
2960, 1593, 1401, 1323, 1258, 1161, 1084, 906, 800 cm–1. 1H NMR (400 MHz, CDCl3, δ, ppm)
7.80 (d, o-CH, J 7.8 Hz, 2H), 7.34 (d, m-CH, J 7.8 Hz, 2H), 2.59 (dd, CHBN, J 8.6, 2.0 Hz, 1H),
2.45 (s, CH3Ph, 3H), 2.04 (d, CHAN, J 5.8 Hz, 1H), 1.88 (dtr, CHN, J 8.6, 5.8 Hz, 1H), -0.04 (s,
13
CH3, 3H). C NMR (100 MHz, CDCl3, δ, ppm) 144.4 (Ci), 135.1 (Cp), 129.6 (Co), 128.1 (Cm),
30.2 (CH2N), 29.3 (CHNH), 21.6 (CH3Ph), -1.33 and 1.37 [CH3 in (R,R+S,S)-diastereomer], -2.1
(CH3 in R,S-diastereoisomer). 29Si NMR (79.5 MHz, CDCl3, δ, ppm) 3.72. Anal. calcd for

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C20H26N2O4S2Si: C, 53.30; H, 5.82; N, 6.22; S, 14.23; Si, 6.23. Found: C, 53.26; H, 5.79; N,
6.21; S, 14.19; Si, 6.22.
4.2.33. Dimethyl{bis[(4-chlorophenyl)sulfonyl]aziridin-2-yl}silane, 20c. Colorless oil. 11%
yield. IR (KBr) 3286, 3092, 2961, 1581, 1475, 1396, 1327, 1163, 1090, 903, 833, 795, 762, 673,
1
626 cm–1. H NMR (400 MHz, CDCl3, δ, ppm) 7.84 (d, o-CH, J 8.5 Hz, 2H), 7.51 (d, m-CH, J
8.5 Hz, 2H), 2.58 (d, CHBN, J 8.6 Hz, 1H), 2.09 (d, CHAN, J 5.9 Hz, 1H), 1.94 (trd, CHN, J 8.0,
6.1 Hz, 1H), -0.09 (s, CH3, 3H), -0.13 (s, CH3, 3H). 13C NMR (100 MHz, CDCl3, δ, ppm) 140.3
(Cp), 136.1 (Ci), 129.4 (Co), 129.3 (Cm), 30.58 (CH2N), 27.1 (CHN), -7.1 and -7.4 (CH3); 29Si
NMR (79.5 MHz, CDCl3, δ, ppm) 1.55. Anal. calcd for C18H20Cl2N2O4S2Si: C, 43.99; H, 4.10;
N, 5.70; S, 13.05; Si, 5.71. Found: C, 43.96; H, 4.08; N, 5.67; S, 12.99; Si, 5.66.
1
Minor diastereomer, H NMR (400 MHz, CDCl3, δ, ppm) 2.58 (d, CHBN, J 8.6 Hz, 1H),
2.04 (d, CHAN, J 5.8 Hz, 1H), 1.94 (trd, CHN, J 8.0, 6.1 Hz, 1H), -0.14 (s, CH3, 3H). 13C NMR
(100 MHz, CDCl3, δ, ppm) 30.49 (CH2N), 27.5 (CHN), -7.5 (CH3). 29Si NMR (79.5 MHz,
CDCl3, δ, ppm) 1.31.
1
4.2.34. Dimethyl{bis[(4-nitrophenylsulfonyl)aziridin-2-yl]silane, 20d. Light-yellow oil. H
NMR (400 MHz, CDCl3, , δ, ppm, from the reaction mixture) 8.42-8.37 (m, o-CH, 2H), 8.17-
8.12 (m, m-CH, 2H), 2.70-2.65 (m, CHBN, 1H), 2.22-2.18 (m, CHAN, 1H), 2.14-2.11 (m, CHN,
1H), -0.03 (s, CH3, 3H).
4.2.35. 3,5-Diiodo-4,4-dimethyl-1-(phenylsulfonyl)-1,4-azasilinane, 21a. White solid. Mp
155 (±2) °C. 4% yield. IR (KBr) 2960, 1451, 1335, 1249, 1161, 1097, 1039, 785, 570 cm–1. 1H
NMR (400 MHz, CDCl3, δ, ppm) 7.78 (d, o-CH, J 7.3 Hz, 2H), 7.61 (tr, p-CH, J 7.3 Hz, 1H),
7.54 (tr, m-CH, J 7.3 Hz, 2H), 4.33 (dd, CHI, J 13.4, 6.1 Hz, 2H), 3.34 (dd, CHBN, J 13.4, 6.1
Hz, 2H), 2.97 (tr, CHAN, J 13.4 Hz, 2H), 0.41 (s, CH3, 3H), 0.26 (s, CH3, 3H). 13C NMR (100
MHz, CDCl3, δ, ppm) 139.3 (Ci), 133.0 (Cp), 129.4 (Co), 126.7 (Cm), 52.6 (CH2N), 6.9 (CHI), -
4.4 and -5.8 (CH3). 29Si NMR (79.5 MHz, CDCl3, δ, ppm) 4.91. Anal. calcd for C12H17I2NO2SSi:
C, 27.65; H, 3.29; N, 2.69; I, 48.69; S, 6.15; Si, 5.39. Found: C, 27.30; H, 3.27; N, 2.53; I, 48.68;
S, 6.01; Si, 5.24.
4.2.36. 3,5-Diiodo-4,4-dimethyl-1-tosyl-1,4-azasilinane, 21b. White solid. Mp 169 °C. 4%
1
yield. IR (KBr) 2960, 2922, 1596, 1455, 1337, 1158, 1097, 1038, 923, 813, 779, 546 cm–1. H
NMR (400 MHz, CDCl3, δ, ppm) 7.66 (d, o-CH, J 8.3 Hz, 2H), 7.33 (d, m-CH, J 8.3 Hz, 2H),
4.31 (dd, CHI, J 12.4, 5.9 Hz, 2H), 3.34 (dd, CHBN, J 13.0, 5.9 Hz, 2H), 2.94 (tr, CHAN, J 13.0
Hz, 2H), 2.44 (s, CH3Ph, 3H), 0.40 (s, CH3, 3H), 0.26 (s, CH3, 3H). 13C NMR (100 MHz, CDCl3,
δ, ppm) 143.9 (Ci), 136.2 (Cp), 130.0 (Co), 126.8 (Cm), 52.6 (CH2N), 21.5 (CH3Ph), 7.0 (CHI), -
4.4 and -5.8 (CH3). 29Si NMR (79.5 MHz, CDCl3, δ, ppm) 5.47. Anal. calcd for C13H19I2NO2SSi:

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C, 29.17; H, 3.58; N, 2.62; I, 47.42; S, 5.99; Si, 5.25. Found: C, 29.10; H, 3.50; N, 2.57; I, 47.22;
S, 5.89; Si, 5.21.
4.2.37. 3,5-Diiodo-4,4-dimethyl-1-((4-nitrophenyl)sulfonyl)-1,4-azasilinane, 21c. White
solid. Mp. 205 (±2) °C. 2% yield. IR (KBr) 2919, 1649, 1579, 1474, 1342, 1248, 1156, 1092,
1
1032, 927, 839, 778 cm–1. H NMR (400 MHz, CDCl3, δ, ppm) 7.72 (d, m-CH, J 8.6 Hz, 2H),
7.51 (d, o-CH, J 8.6 Hz, 2H), 4.29 (dd, CHI, J 12.6, 5.5 Hz, 2H), 3.34 (dd, CHBN, J 13.2, 5.5 Hz,
2H), 2.97 (tr, CHAN, J 13.2 Hz, 2H), 0.42 (s, CH3, 3H), 0.27 (s, CH3, 3H). 13C NMR (100 MHz,
CDCl3, δ, ppm) 139.6 (Cp), 137.7 (Ci), 129.7 (Co), 128.2 (Cm), 52.6 (CH2N), 6.6 (CHI), -4.4 and
-5.8 (CH3). 29Si NMR (79.5 MHz, CDCl3, δ, ppm) 5.30. Anal. calcd. for C12H16ClI2NO2SSi: C,
25.94; H, 2.90; N, 2.52; I, 45.68; S, 5.77; Si, 5.05; found: C, 25.91; H, 2.88; N, 2.50; I, 45.59; S,
5.69; Si, 5.01.
4.2.38. 3,5-Diiodo-4,4-dimethyl-1-((4-nitrophenyl)sulfonyl)-1,4-azasilinane, 21d. White
solid, Mp 244 °C. 2% yield. IR (KBr) 3102, 2922, 1736, 1523, 1459, 1345, 1161, 1096, 1037,
785, 593 cm–1. 1H NMR (400 MHz, CDCl3, δ, ppm) 8.38 (d, m-CH, J 8.6 Hz, 2H), 7.97 (d, o-
CH, J 8.6 Hz, 2H), 4.31 (dd, CHI, J 12.6, 6.0 Hz, 2H), 3.36 (dd, CHBN, J 13.2, 6.0 Hz, 2H), 3.03
(tr, CHAN, J 13.0 Hz, 2H), 0.40 (s, CH3, 3H), 0.29 (s, CH3, 3H).
4.3. X-ray measurements
Crystal data were collected on a Bruker D8 Venture diffractometer with MoKα radiation (λ
= 0.71073) using the φ and ω scans. The structures were solved and refined by direct methods
using the SHELX programs set.46 Data were corrected for absorption effects using the multi-scan
method (SADABS). Nonhydrogen atoms were refined anisotropically using SHELX programs
set.46 The details of all structures can be obtained free of charge from the Cambridge
Crystallographic Data Centre viawww.ccdc.cam.ac.uk/data_request/cif.
Conflict of interest
The authors declare no conflict of interest.
Supporting Information
Experimental details, spectroscopic data and X-ray structural information for new compounds
(CCDC 1882243 (10d), 1859983 (18d), 1815954 (21a), 1859981 (21b), 1874187 (21c),
1859982 (21d)). This material is available free of charge via the Internet at doi:
Acknowledgement
This work was performed using the equipment of the Baikal Analytical Center for Collective
Use of SB RAS and supported by RFBR Grants 17-03-00213 and 18-33-20131.

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•
Vinyl silanes undergo via oxidative addition and heterocyclization when reacting with
sulfonamides in oxidative conditions.
•
•
The reactivity of triflamide is principally different from that of arenesulfonamides.
Silylated mono- and diaziridines, N-sulfonyl-1,4-azasilinanes and 3-(triflyl)-5-
(triflamido)oxazolidine are obtained.