Insights for diastereoselective synthesis of cyclic α-sulfinyl and sulfanyl oximes

Article abstract of DOI:10.1016/j.tetlet.2017.04.083

The comparison in several reaction conditions for synthesis of nonracemic α-methylsulfinylation of 3,4-dihydronaphthalen-1(2H)-one was achieved. The sulfanylation reactions of 3,4-dihydronaphthalen-1(2H)-one-O-methyloxime and 2-(methylsulfinyl)-3,4-dihydronaphthalen-1(2H)-one-O-methyloxime by homogenous reaction medium are reported. The products were obtained in good yields and de. The yields, diastereoselectivity and theoretical calculations to all obtained compounds to support the experimental data are compared and discussed.

Full text of DOI:10.1016/j.tetlet.2017.04.083

Accepted Manuscript
Insights for diastereoselective synthesis of cyclic α-sulfinyl and sulfanyl oximes
Gislaine Aparecida Honorato, Ricardo Vieira de Lima, Bhaskar Reddy Manda,
Derisvaldo Rosa Paiva, Tairine Pimentel, Roberto da Silva Gomes
PII:
S0040-4039(17)30538-5
DOI:
http://dx.doi.org/10.1016/j.tetlet.2017.04.083
TETL 48875
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
12 March 2017
21 April 2017
24 April 2017
Please cite this article as: Honorato, G.A., de Lima, R.V., Manda, B.R., Paiva, D.R., Pimentel, T., Gomes, R.d.S.,
Insights for diastereoselective synthesis of cyclic α-sulfinyl and sulfanyl oximes, Tetrahedron Letters (2017), doi:
http://dx.doi.org/10.1016/j.tetlet.2017.04.083
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Insights for diastereoselective synthesis of
cyclic α-sulfinyl and sulfanyl oximes
Gislaine Aparecida Honorato, Ricardo Vieira de Lima, Bhaskar Reddy Manda, Derisvaldo Rosa Paiva, Tairine
Pimentel and Roberto da Silva Gomes*

1
Tetrahedron Letters
journal homepage: www.elsever.c om
Insights for diastereoselective synthesis of cyclic α-sulfinyl and sulfanyl oximes
Gislaine Aparecida Honoratoa, Ricardo Vieira de Limaa, Bhaskar Reddy Mandab, Derisvaldo Rosa Paivac,
Tairine Pimentelb and Roberto da Silva Gomesa,b*
aFaculty of Exact Sciences and Technology-FACET, Federal University of Grande Dourados-UFGD. Rodovia Dourados-Itahum, km 12 - Dourados, MS, zip
code: 79804-970, Brazil.
bInstituto de Química, Universidade Federal de Mato Grosso do Sul, Cidade Universitária S/N, Campo Grande, Mato Grosso do Sul (MS), 79070-900, Brazil.
cCEFET-RJ, Campus Valença, Rua Voluntários da Pátria, Valença, Rio de Janeiro, 27600-000, Brazil.
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
The comparison in several reaction conditions for synthesis of nonracemic α-methylsulfinylation
of 3,4-dihydronaphthalen-1(2H)-one was achieved. The sulfanylation reactions of 3,4-
dihydronaphthalen-1(2H)-one-O-methyloxime and 2-(methylsulfinyl)-3,4-dihydronaphthalen-
1(2H)-one-O-methyloxime by homogenous reaction medium are reported. The products were
obtained in good yields and de. The yields, diastereoselectivity and theoretical calculations to all
obtained compounds to support the experimental data are compared and discussed.
Available online
Keywords:
2009 Elsevier Ltd. All rights reserved.
Asymmetric synthesis
Sulfinylation
Sulfanylation
Diastereoselectivity
Introduction of sulfur functionality into organic molecules is
an important process for the drug development1-5 and fine
chemical synthesis6-8. The sulfanylation of β-ketosulfoxides have
shown to be important intermediates owing to fact that the
obtained sulfoxides can be used as chiral auxiliaries in
asymmetric synthesis9-11, as efficient stereoselective inductors12-
14, in Diels-Alder reaction15-17 in the C-C bond formation
(methylsulfinyl)-2-(methylsulfanyl)-3,4-dihydronaphthalen-
1(2H)-one-O-methyl oxime 6. The target compound was planned
to be obtained by the below disconnection, starting from a
simpler and inexpensive starting material.
OCH3
OH
N
O
N
O
S
O
O
S
O
O
S
O
S
reactions,18-21 and drug candidates22,23
.
S
S
S
6
5
4
3
1
Literature reports of both homogeneous and heterogeneous
transfer sulfanylation methods are comparable in terms of yield
and diastereoselectivity24-26. Generally, the β-ketosulfoxides can
be achieved by the reaction between a chiral sufinyl anion and an
a cyclic ketone is used, the β-
ketosulfoxides are not accessible.
Scheme 1. Retrosynthesis of novel 2-(methylsulfinyl)-2-
(methylsulfanyl)-3,4-dihydronaphthalen-1(2H)-one-O-methyl oxime
6.
ester,24b however when
The compound 6 could be obtained from oxime 5. The oxime
5 can be prepared from 2-sulfinyl-2-sulfanyl ketone 4, which
could be formed from α-sulfinyl ketone 3 which in turn could be
In a previous communication, we reported the sulfanylation of
2-(methylsulfinyl)-2,3-dihydro-1H-inden-1-one by phase transfer
catalysis using benzyltriethylammonium chloride (TEBAC) as
catalyst as well as in homogeneous conditions furnish the
products in good yield and in high disatereoisomeric excess
(de).27
prepared
from
the
commercially
available
3,4-
dihydronaphthalen-1(2H)-one
1
as an inexpensive starting
material.
Asymmetric oxidation of sulphides29,30 by using of Sharpless
reagent [titanium tetraisopropoxide (TTIP)], (R,R) diethyl tartrate
(DET) and tert-butyl hydrogen peroxide (TBHP) was carried out,
achieving 3 (Scheme 2, conditions a) with 50 % yield, 10% of ee
As part of our general program of exploring the scope of
sulfanylation by the utilization of either PTC or homogeneous
method led us to investigate the sulfanylation of 3,4-
dihydronaphthalen-1(2H)-one as well as 3,4-dihydronaphthalen-
1(2H)-one-O-methyl oxime. In this context, an efficient
1
and 50 % of de, calculated by H NMR shifts of methylsulfinyl
hydrogens by using Kagan’s reagent between 3.85-3.87 ppm31.
nonracemic
synthetic
route
for
2-(methylsulfinyl)-2-
To improve the preparation of optically active 3, a direct
(methylsulfanyl)-3,4-dihydronaphthalen-1(2H)–one-O-methyl
oxime is reported.
condensation of 3,4-dihydronaphthalen-1(2H)-one
1
with
methylsulfinyl chloride as methysulfinyl donor with LDA as
bulky base was performed (Scheme 2, conditions b).
In contribution to synthetically useful building blocks,
Scheme
1 illustrates the retrosynthetic analysis of 2-

2
O(1)-C(2)-C(3)-S(4)
C(2)-C(3)-S(4)-O(5)
O(1)-C(2)-C(3)-C(6)
α =
β =
γ =
O
O
O
S
O(1)-C(2)-C(13)-C(12)
C(2)-C(3)-C(6)-C(7)
δ =
ω =
1
3
Scheme 2: Synthetic method for the compound 3: a) 1)
CH3SSO2CH3, LDA; 2) Ti[O(i-pr)]4, (R,R)-DET, CH2Cl2, TBHP; b)
CH3SOCl, LDA, THF.
Scheme 4. Atoms labelling and definition of relevant dihedral angles
of 3.
Our approach was diastereoselective and the yield was 67%,
10% ee and 71% de which was calculated from the relative
Table 1: Comparison between relative energy (Kcal mol-1), population (P),
dipole moment (µ, D) and selected dihedral (O) for the minimum energy
conformations of 3 at the B3LYP/6-311+G(d,p) level of theory.
1
integration of H NMR signals corresponding to methylsulfinyl
groups at δ 2.72 ppm and 2.96 ppm for the majority and minority,
respectively, using Kagan´s reagent and this route showed to be
better in comparison to that one described in the literature26.
Comp.
Ea
µ
Dihedral Angleb
α
β
γ
δ
ω
(SS-C2R)-3
(SS-C2S)-3
0.00
6.42
2.77
6.71
-77.1
16.1
-40.4
30.7
161.9
145.5
-5.2
5.2
46.9
57.8
To obtain the diastereomerically enriched 3, the reaction was
performed
employing
1,2:5,6-di-O-isopropylidene-α-D-
glucofuranosyl-(-)-(SS)-methane-sulfinate ((SS)-MeSO2-DAG)
(Scheme 3) as chiral sulfinylating agent10,11. In this approach we
obtained 72% yield, 11% of ee and 76% of de of (SS)-3 as a
mixture of epimers (7:3) providing a new stereogenic center of
known absolute configuration (Scheme 3).
aRelative energy;
bSee Scheme 4
The less stable one (SS-C2S)-3 (Erel= 6.42 kcal mol-1; µ=6.71
D) which S-configuration for C2 displays the S=O (α= 16.1o)
substituent in a syn-clinal geometry with respect to carbonyl
group which allows two short intramolecular contacts less than
O
O
O
S
(SS)MeSO2-DAG)
CH3
the
ΣvdW
between
the
oppositely
charged
LDA/THF
Oδ-(1)[CO]…Sδ+(4), ∆l≅-0.48 Å and Oδ-(1)[CO]…Hδ+(26), ∆l≅-0.26
Å. These short contacts in SS-C2R-3 contribute three attractive
electrostatic interactions (hydrogen bond) for the referred
compound in comparison to less stable SS-C2S-3 which in turn
possesses only two hydrogen bonds.
1
3
Scheme 3. New methylsulfinylation approach using ((SS)-MeSO2-
DAG) to obtain optically active 3.
The influence of steric and electronic effects on the
conformational properties are essential to rationalize the
stereocontrol of this reaction considering both possibilities (SS-
C2R or SS-C2S)-3 for nucleophilic attack of 1. Furthermore,
These results prompted us to affirm that the attack of enolate
to ((SS)-MeSO2-DAG) favors the more thermodynamically
stable (SS-C2R)-3 and is due to the diastereoselectivity imposed
by the asymmetric induction of the MeSO- group present in
((SS)-MeSO2-DAG), increasing the formation of (SS-C2R)-3 in
comparison to (SS-C2S)-3 (Figure 2).
1
aiming to confirm our stereochemical assignment of H NMR
spectra, a density functional theory (DFT) calculation was
performed. Theoretical calculations for compound 3 indicates
that the more stable (SS-C2R)-3 (Erel=0.00 kcal mol-1; µ=2.77 D)
R-configuration C2 displays the S=O (α= -77.1o) substituent in a
syn-periplanar geometry with respect to the carbonyl group
(Figure 1). This geometry allows the following short
intramolecular contacts between the oppositely charged
(SS)-MeSO2-DAG)
Oδ-(1)[CO]…Sδ+(4);
Oδ-(1)[CO]…Hδ+(both
15,16,17);
Oδ-
(1)[CO]…Hδ+(26) and Oδ-(5)[SO]…Hδ+(21) atoms, which are shorter
than the sum of the van der Waals radii (ΣvdW) by ∆l≅-0.01 Å,
∆l≅-0.29 Å, ∆l≅-0.27 Å and ∆≅-0.27 Å, respectively.
O
1
H
S
S
O
H
O
O
O
3
(SS,2R)-3
majority
(SS,2S)-
minority
Figure 2. Staggered representation of sulfanylation of 1 via
nucleophilic attack.
The α-methylsulfanylation reaction of SS-C2R-3 was
conducted by reaction in phase transfer catalysis (PTC)
conditions using S-methyl methanesulfonothioate, K2CO3 and
TEBAC in CH2Cl2/C6H6 medium at room temperature to achieve
the 2-(methylsulfinyl)-2-(methylsulfanyl)-3,4-dihydronaphthalen
-1(2H)-one 4 in 38% yield with 90% de. The major diastereomer
of 4 was isolated by chromatographic separation in 38% yield.
The reaction of 4 with hydroxylamine hydrochloride in presence
of NaOAc in toluene at reflux28 was conducted to prepare the
targeted compound (Scheme 5). However, this reaction did not
occur, possibly due to the lack of α-proton for enolization.
(SS-C2S)-3
(SS-C2R)-3
Figure 1. Selected minimum energy conformations and
intramolecular contacts for 3 (for atom labelling, see Scheme 4) at
the B3LYP/6-311+G(d,p) level of theory.

3
respect to the oximic group and configuration (S) for C2. This
conformation allows the attractive intramolecular contacts
O
O
S
O
O
S
S
Nδ-
K2CO3, TEBAC,
MeSSO2Me
NH2OH.HCl,
NaOAc
(hydrogen bond) between the oppositely charged
(1)[CN]…Hδ+(26); Oδ-(30)[NO]…Hδ+(18); Oδ-(5)[SO]…Hδ+(19) and
Oδ-(5)[SO]…Hδ+(20) atoms, whose are shorter than the ΣvdW radii
by ∆l≅-0.15 Å, ∆l≅-0.28 Å, ∆l≅-0.26 Å and ∆l≅-0.28 Å,
respectively, the oppositely charged short intramolecular contact
between Oδ-(30)[NO]…Sδ+(4) atoms, ∆l≅-0.25 Å and one repulsive
short contact between Sδ+(4)…Hδ+(20) atoms, ∆l≅-0.17 Å.
No reaction
toluene, 110 o
C
CH2Cl2/C6H6, rt, 3h
3
4
Scheme 5. Attempting for the synthesis of compound 6.
To overcome this synthetic problem, different chemical
conditions and synthetic strategies have tested. Scheme 6
describes the retrosynthetic analysis leading to the key
intermediates for the synthesis of targeted molecule. The required
compound 6 could be obtained by α-methylsulfanylation of α-
methylsulfinyl naphthone 7 which in turn can be prepared by the
α-methylsulfanylation of compound 8. This corresponds to a
decision that thiolated groups can be added late. Then, the
compound 8 can be prepared by methylation of 9 prepared by the
corresponding naphthone 1 which can be chosen again as a
starting material.
The less stable conformer (SS-C2R-7) (Erel=5.84 kcal mol-1;
µ=3.38 D) present configuration (R) for C2 and the S=O
(α= -96.3o) substituent is in an anti-clinal geometry with respect
to the oximic group. Similarly to SS-C2S-7, the geometry of SS-
C2R-7 allows four oppositely charged short intramolecular
contact (hydrogen bond) between Nδ-(1)[CN]…Hδ+(26), ∆l≅-0.31
Å; Oδ-(30)[NO]…Hδ+(18), ∆l≅-0.43 Å; Oδ-(5)[SO]…Hδ+(19), ∆l≅-
0.29 Å and Oδ-(30)[NO]…Hδ+(both 15,16,17) atoms, but allows one
important repulsive short contact between Sδ+(4)…Hδ+(19), ∆l≅-
0.15 Å atoms and as consequence, a significant Coulombic
repulsion of these atoms arises, which act destabilizing this
conformer.
OCH3
OCH3
OCH3
OH
N
N
O
N
O
N
O
S
S
S
6
7
8
9
1
Scheme 6. New retrosynthetic proposal of 2-(methylsulfinyl)-2-
(methylsulfanyl)-O-methyl oxime.
The reaction of commercially available tetralone 1 with
hydroxylamine hydrochloride in ethanol in presence of NaOAc
under reflux achieved the oxime 9 in quantitative yield32. The
obtained oxime was subjected to O-methylation with MeI and
afforded the 3,4-dihydronaphthalen-1(2H)-one-O-methyloxime
in 92% yield33 (Scheme 7).
(SS-C2S)-7
(SS-C2R)-7
OH
OCH3
O
N
N
Figure 3. Selected minimum energy conformations and
intramolecular contacts for 7 (for atom labelling, see Scheme 9) at
the B3LYP/6-311+G(d,p) level of theory.
NH2OH.HCl,
NaOAc
MeI
EtOH, 78 o
C
1
9
8
28H
29
H
27
H
Scheme 7. Synthesis of methyloxime 8.
14C
O30
O 5
The methylsulfinylation was performed using the same
methodology of compound 3 synthesis (Scheme 3). However, the
use of oxime 8 in LDA/THF leads to ketone 3, then, the system
base/solvent was changed by NaH as small base in DMSO26
(Scheme 8) and the 2-methylsulfinyl-O-methyl-oxime 7 with
known stereogenic center was obtained after chromatographic
purification in 69% yield, 12% ee and 75% de.
The 1H NMR spectral analysis of the crude product allowed to
conclude that the formation of a diastereomeric mixture (90:10),
confirmed by the presence of one signal related to the SOCH3 at
2.66 ppm and a triplet at δ 4.77 ppm (J = 4 Hz) corresponding to
methine hydrogen.
1
H 26
C12
N
H15
N(1)-C(2)-C(3)-S(4)
C(2)-C(3)-S(4)-O(5)
O(30)-N(1)-C(2)-C(3)
C(2)-C(3)-C(6)-C(7)
N(1)-C(2)-C(13)-C(12)
α =
β =
γ =
δ =
ω =
16
H
S
4
C
25 H
2 C
3
11
C
13
C
17
H
C
18
H
H19
10C
C
8
C
6
24H
9C
23 H
C7
H20
H
H 21
22
Scheme 9. Atoms labelling of 2-methylsulfinyl-O-methyl-oxime 7
and definition of relevant dihedral angles.
Table 2: Comparison between relative energy (Kcal mol-1), dipole moment
(µ, D) and selected dihedral (O) for the minimum energy conformations of 7
at the B3LYP/6-311+G(d,p) level of theory.
Comp.
Ea
µ
Dihedral Angleb
OCH3
OCH3
α
β
γ
δ
ω
N
O
S
N
(SS-C2S)-7
(SS-C2R)-7
0.00
5.84
3.71
3.38
66.0
-96.3
158.0
-158.0
-3.33
1.83
33.9
52.1
-29.3
9.36
(SS)MeSO2-DAG)
CH3
aRelative energy;
NaH/DMSO
bSee Scheme 9
7
8
Scheme 8. Synthesis of methylsulfinyl oxime 7.
In summary, the lowest Coulombic repulsive effect combined
with the stabilizing effect of Oδ-(30)[NO]…Sδ+(4) atoms and four
hydrogen bonds in (SS-C2S-7) thermodynamically favors the
formation of this conformer in comparison to the two Coulombic
repulsive effect which destabilizing in a higher intensity in (SS-
C2R-7), even with its four hydrogen bonds. These results allowed
us to consider that the nucleophilic attack occur in (SS, C2R)-7
preferably compared to (SS, C2S)-7.
To understand this diastereoselectivity,
calculations using density functional theory (DFT) calculation
was performed for 7 (Figure 3, Scheme 9, Table 2).
theoretical
Theoretical calculations for 7 indicate the more stable
conformer (SS, C2S-7) (Erel=0.00 kcal mol-1; µ=3.71 D) present
the S=O (α= 66.0o) substituent in a syn-clinal geometry with

4
8. Tao, X. L.; Boyer, C.; Lowe, A. B.; Davis, T. P.
To get the further carbonyl functionality at α-position, it is
needed the methylsulfanylation at α-position. The reaction of 7
with S-methyl methanesulfonothioate using K2CO3 as base and
N-Benzylquininium chloride (QUIBEC) as catalyst in
CH2Cl2:C6H6 (1:1) was carried out to afford the compound 6
(Scheme 10a). However, this reaction did not occur which can be
rationalized due to the N-benzylquininium substituent (bulk
substituent) present in QUIBEC catalyst which hinders the attack
of the sulfinylating agent.
Macromolecules, 2010, 43, 20-24.
9. Wladislaw, B.; Marzorati, L.; Biaggio, F. C.; Vargas, R. R.;
Bjorklund, M. B.; Zukerman-Schpector, J. Tetrahedron, 1999, 55,
12023-12030.
10. Rodrigues, A.; Wladislaw, B.; Di Vitta, C.; Filho, J. E. P. C.;
Marzorati, L.; Bueno M. A.; Olivato, P. R. Tetrahedron Lett.,
2010, 51, 5344-5348.
11. I. Fernandez, N. Khiar, J.; Llera, M.; Alcudia, F. J. Org. Chem.,
1992, 57, 6789-6796.
12. Corey, E. J.; Chaykowski, M. J. J. Am. Chem. Soc., 1962, 84, 867-
868.
13. Kunieda, N.; Nokami, J.; Kinoshita, M. Chem. Lett., 1974, 369-
t
Consequently, the homogeneous conditions using BuLi as
o
372.
base with S-methyl methanesulfonothioate in THF at -78 C was
14. a) Schneider, F.; Simon, R. Synthesis, 1986, 582; b) Carrefio, M.
C.; Ruano, J. L. G.; Rubio, A. Tetrahedron Lett., 1987, 28, 4861-
4864.
15. Mancheño, O. G.; Arrayás, R. G.; Carretero, J. C. J. Am. Chem.
Soc., 2004, 126, 456-457.
16. Jagt, J. C.; Van Leusen, A. M. J. Org. Chem., 1974, 39, 564-566.
17. Han, B.; Li, J.; Ma, C.; Zhang, S.; Chen, Y. Angew. Chem. Int.
Ed., 2008, 120, 10119-10122.
carried
out
and
afforded
the
2-(methylsulfinyl)-2-
(methylsulfanyl)-O-methyl oxime 6. The product was obtained in
50% yield as a mixture of diastereomers, illustrated by the
1
analysis of H NMR of the crude reaction mixture in which two
simplets was observed at δ 2.50 ppm and 2.21 ppm, referring to
the methyl groups using Kagan´s reagent.
18. Tsuchihashi, G.; Mitamura, S.; Inoue, S.; Ogura, K. Tetrahedron
Lett., 1973, 14, 323-326.
19. Posner, G. H.; Mallamo, J. P.; Miura, K. J. Am. Chem. Soc., 1981,
103, 2886-2888.
20. Pyne, S. G.; Bloem, P.; Chapman, S. L.; Dixon, C. E.; Griffith, R.
J. Org. Chem., 1990, 55, 1086-1093.
21. Davis, R.; Kern, J. R.; Kurz, L. J.; Pfister, J. R. J. Am. Chem. Soc.,
1988, 110, 7873-7874.
a) K2CO3, QUIBEC,
CH3SSO2CH3
OCH3
no reaction
OCH3
N
O
CH2Cl2/C6H6
S
N
O
S
b) tBuLi,
7
CH3SSO2CH3
S
THF, -78 oC
6
22. Parsons, W. J.; Ramkumar, W.; Stiles, G. L. Mol. Pharmacol.,
1988, 33, 441-448. TIRAR 22 E 23
Scheme 10. Synthesis of targeted molecule 6 in (a) PTC and (10b)
23. Kutter, E.; Austel, V. Arzneimittelforschung, 1981, 31, 135-141.
24. a) Ruano, J. L. G.; Barros, D.; Maestro, M. C.; Arava-Maturana,
R. Fischer, J. J. Org. Chem., 1996, 61, 9462-9470. b) Kunieda, N.;
Nokami, J.; Kinoshita, M. Chem. Lett., 1974, 377-380
25. Ruano, J. L. G.; Barros, D.; Maestro, M. C.; Alcudia, A.;
Fernandez, I. Tetrahedron: Asymmetry, 1998, 9, 3445-3453.
26. Bianchi, T. A.; Cate, L. A. J. Org. Chem., 1977, 42, 2031–2032.
27. Paiva, D. R.; Gomes, R. S. Orbital: The Electronic Journal of
Chemistry, 2013, 5, 56-63.
homogeneous phase.
Conclusions
In conclusion, a single step sulfinylation reaction of 1-
tetralone is conceived in good yield. A convenient method for
diastereoselective sulfanylation of 3,4-dihydronaphthalen-1(2H)-
one-O-methyl
oxime
and
2-(methylsulfinyl)-3,4-
28. Deshmukh, M.; Duñach, E.; Juge, S.; Kagan, H. B. Tetrahedron
dihydronaphthalen-1(2H)-one-O-methyl oxime has also been
achieved. We have shown that the homogeneous reaction
medium is a viable method over phase transfer catalysis for
sulfanylation.
Lett., 1984, 25, 3467-3470
29. Pitchen, P.; Kagan, H. B. Tetrahedron. Lett., 1984, 25, 1049–
1052.
30. Pitchen, P.; Dunach, E.; Deshmukh, M. N.; Kagan, H. B. J. Am.
Chem. Soc., 1984, 106, 8188-8193.
31. See suplemmentary information.
Acknowledgement
32. Wladislaw, B.; Bueno, M. A.; Marzorati, L.; Di Vitta; C.;
Zukerman-Schpector, J. J. Org. Chem., 2004, 69, 9296-9298.
33. Douglass, I. B.; Norton, R. V. J. Org. Chem., 1968, 33, 2104-
2106.
Brazilian authors thank to Fundação de Apoio ao
Desenvolvimento de Ensino, Ciência e Tecnologia do Estado do
Mato Grosso do Sul (Fundect) and to Conselho Nacional de
Desenvolvimento Científico e Tecnológico for the financial
support offered for this research (R.S.G. CNPq- 459654/2014-4)
and for the scholarship for T.P. and G.A.H. and B.R.M. thank for
the fellowship to Coordenação de Aperfeiçoamento de Pessoal de
Nível Superior (CAPES).
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5
Highlights
• A single step sulfinylation reaction of 1-tetralone
is conceived in good yield.
• A convenient method for diastereoselective
sulfanylation of cyclic ketones and oximes has
been achieved.
• The homogeneous reaction medium is a viable
method over phase transfer catalysis for
sulfanylation.
• Stereoselectivity was discussed and compared using
1H NMR technique.
• Theoretical
calculations
explain
the
diastereoselectivity and stereocontrol.