Diastereodivergent Synthesis of 2-Ene-1,4-hydroxy Sulfides from 2-Sulfinyl Dienes via Tandem Sulfa-Michael/Sulfoxide-Sulfenate Rearrangement

Article abstract of DOI:10.1021/acs.orglett.0c03929

The highly diastereoselective sulfa-Michael addition of thiolates to enantiopure 2-sulfinyl dienes leads to anti or syn 2-ene-1,4-hydroxy sulfides in good yields and selectivities dependent on the reaction conditions in a diastereodivergent process. Synthetic applications of these enantiopure hydroxy sulfides by subsequent sigmatropic rearrangements have been outlined.

Full text of DOI:10.1021/acs.orglett.0c03929

pubs.acs.org/OrgLett
Letter
Diastereodivergent Synthesis of 2‑Ene-1,4-hydroxy Sulfides from
2‑Sulfinyl Dienes via Tandem Sulfa-Michael/Sulfoxide-Sulfenate
Rearrangement
́
Marina Velado, Roberto Fernandez de la Pradilla, and Alma Viso*
Cite This: https://dx.doi.org/10.1021/acs.orglett.0c03929
Read Online
sı
*
Metrics & More
Article Recommendations
Supporting Information
ACCESS
ABSTRACT: The highly diastereoselective sulfa-Michael addition
of thiolates to enantiopure 2-sulfinyl dienes leads to anti or syn 2-
ene-1,4-hydroxy sulfides in good yields and selectivities dependent
on the reaction conditions in a diastereodivergent process. Synthetic
applications of these enantiopure hydroxy sulfides by subsequent
sigmatropic rearrangements have been outlined.
he asymmetric sulfa-Michael addition is a particularly
useful, general, and versatile method to prepare carbon−
F.8 The possibility of benefiting from the useful reactivity of
enantiopure allylic sulfides F in highly stereocontrolled
processes entailing sigmatropic rearrangements was an addi-
tional point of interest to embark on this study.5,9−11
In this report, we summarize our preliminary results on the
stereocontrolled addition of thiolates to enantiopure 2-sulfinyl
dienes followed by [2,3]-sigmatropic rearrangement and
sulfenate cleavage to produce anti or syn hydroxy allylic
sulfides F at will, in good yields and selectivities. In addition,
further synthetic applications of allylic sulfides F in subsequent
sigmatropic processes via allylic sulfoxides, sulfilimines, and
sulfur ylides have been explored.
T
sulfur bonds, of considerable importance in biological
processes, material science, medicinal chemistry, and synthetic
methodologies.1 Within this field, thiol or thiolate additions to
substituted alkenyl sulfoxides are relatively rare and unselective
in some cases.2 In recent years we have been involved in the
application of readily available 1-sulfinyl dienes A3 and 2-
sulfinyl dienes C4 (X = O, NTs, NR′; Y = O, NR′; Scheme 1)
Scheme 1. Cascade Processes for Syntheses of 2-Ene-1,4-
difunctionalized Products
2-Sulfinyl dienes 2a−h were selected for this study to
address the influence of aryl and alkyl substitution, need for
hydroxyl protection, and geometry of the dienes. These
substrates have been synthesized from enantiopure 1-iodo
vinyl sulfoxides, originally prepared from (1R,2S,5R)-
(−)-menthyl (S)-p-toluenesulfinate, by Stille coupling7 or
coupling with vinyl boronic acids.6c
Table 1 summarizes our efforts directed to examine the
viability and selectivity of the proposed tandem conjugate
addition/[2,3]-sigmatropic rearrangement (for full details, see
Supporting Information (SI)). We selected diene (E,Z)-2a,
octanethiol, and benzyl thiol in the presence of NaH and n-
BuLi in toluene, in analogy with previous results on alkoxide
additions.6c After some experimentation, we found that sodium
and lithium octyl thiolates afforded the desired 2-ene-1,4-
hydroxy sulfide anti-3a in good yield and excellent diaster-
in stereoselective synthesis, including the conjugate addition of
amines and alkoxides (R3YH, RXH) to produce allylic
sulfoxide intermediates that underwent a [2,3]-sigmatropic
rearrangement,5 ultimately leading to 1,4-diol or 1,4-amino-
alcohol derivatives B in a cascade process, with good yields and
stereoselectivities.6 These results prompted us to examine the
conjugate addition of thiolates to 2-sulfinyl dienes D, readily
available from iodides or stannanes 1 (Scheme 1),7 that could
afford allylic sulfoxides E, and ultimately lead to allylic sulfides
Received: November 27, 2020
https://dx.doi.org/10.1021/acs.orglett.0c03929
© XXXX American Chemical Society
Org. Lett. XXXX, XXX, XXX−XXX
A

Organic Letters
pubs.acs.org/OrgLett
Letter
Table 1. Optimization of the Tandem Thiolate Conjugate Addition/[2,3]-Sigmatropic Rearrangement
ab
,
c
entry
compd
RSH
octylSH
octylSH
octylSH
BnSH
BnSH
BnSH
PhSH
MeOC6H4SH
MeOC6H4SH
octylSH
BnSH
base/temp/time
anti/syn
3a:4a 97:3
yield
1
2
3
4
5
6
7
8
(E,Z)-2a
(E,Z)-2a
(E,Z)-2a
(E,Z)-2a
(E,Z)-2a
(E,Z)-2a
(E,Z)-2a
(E,Z)-2a
(E,Z)-2a
(E,E)-2a
NaH/0 °C−rt/1 h
BuLi/0 °C−rt/3 h
20%DBU/rt/20 h
NaH/0 °C−rt/2 h
BuLi/0 °C−rt/3 h
BuLi/45 °C/2 h
NaH/0 °C−rt/3 h
NaH/0 °C−rt/3 h
BuLi/0 °C−rt/2 h
BuLi/0 °C−rt/24 h
BuLi/0 °C−rt/20 h
88%
86%
50%
99%
80%
87%
71%
90%
53%
76%
78%
3a:4a 97:3
3a:4a 95:5
3b:4b 67:33
3b:4b 75:25
3b:4b 90:10
3c:4c 9:91
3d:4d 9:91
3d:4d 67:33
d
9
10
11
3a:(ent-4a:4a) 0:(88:12)
3b:(ent-4b:4b) 10:(81:9)
(E,E)-2a
a
b
1
Measured from the H NMR of the reaction mixture. Absolute configuration at C-2 was determined as (S)-MPA esters 5 and 6 (see SI).
Combined yield of 3 and 4. Minor amounts (5%) of (E,E)-2a were detected in the H NMR of the reaction crude.
c
d
1
eoselectivity (anti/syn, 97:3). Other reaction conditions such
as the addition of octanethiol in the absence of a base did not
produce any addition product and DBU, frequently used as an
initiator in sulfa-Michael reactions,12 gave anti-3a in lower
yield (Table 1, entries 1−3). In contrast to octanethiol, benzyl
thiol using NaH or n-BuLi as bases led to a decrease in anti/syn
selectivity that interestingly was improved by raising the
reaction temperature to 45 °C (entries 4−6) to produce anti-
3b in good yield and diastereoselectivity (87%, 90:10).
In sharp contrast, the use of aromatic thiols and NaH led to
good yields and selectivities of syn 1,4-hydroxy sulfides 4c and
4d (9:91) with opposite configuration at C-2 determined by
analysis of their (S)-MPA derivatives (see SI) (Table 1, entries
7 and 8). This stereochemical outcome was reversed with the
lithium thiolate albeit in moderate selectivity to produce
predominantly anti-3d (Table 1, entry 9). Finally, treatment of
less reactive diene (E,E)-2a with LiSoctyl and LiSBn was
examined in slower reactions (20−24 h) to produce
predominantly syn products with lower enantiomeric ratios
(Table 1, entries 10 and 11). Also, lower conversions and
selectivities were observed for diene (E,E)-2a using sodium
aryl thiolates (see, SI).13
Scheme 2. Scope for the Reaction of Alkyl and Benzyl
Thiolates
a
Encouraged by these preliminary results we continued this
study by focusing on octyl and benzyl thiolates and a variety of
sulfinyl dienes with Z geometry at the sulfoxide bearing double
bond, and the results obtained are summarized in Scheme 2. In
addition, to 3a and 3b, discussed in Table 1, installing a TIPS
silyl ether at the allylic alcohol produced excellent diaster-
eoselectivities affording 3e and 3f. The addition is compatible
with a homoallylic hydroxyl group in 2c to afford 3g in good
yield and more demanding sterically or electronically sulfinyl
dienes 2d, 2e, and 2f are also viable substrates for this
chemistry by using lithium thiolates (3h−3j, 4k). In contrast
with the addition of oxygen nucleophiles,6c 2-sulfinyl dienes 2g
and 2h with an alkyl substituent at the position that undergoes
the thiolate conjugate addition (R1 = Bu) produced good
yields of the anti products 3l, 3m, and 3n with good to
excellent diastereoselectivities. Interestingly, the use of sodium
thiolates in some cases decreases the amount of anti-3 in the
mixture. Finally, we examined briefly the use of N-Boc cysteine
a
Conditions: The reaction was performed from 0 °C to rt unless
b
otherwise stated. The absolute configuration of 3 and 4 was
determined from the MPA esters 5 and 6 (see SI). Dr expressed as
anti/syn ratio. Combined yield. Minor byproducts were also isolated
(20%) and characterized (see SI). A 5% of (E,E)-2a was also detected
c
d
e
f
in the crude reaction mixture.
B
https://dx.doi.org/10.1021/acs.orglett.0c03929
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
pubs.acs.org/OrgLett
Letter
methyl ester as a representative example of a more function-
alized thiol, and after some experimentation, adduct 4o was
obtained in acceptable yield and fair selectivity, along with
Scheme 4. Synthesis of Triol and Hydroxy Sulfonamido
Derivatives
a
1
minor amounts (5%) of (E,E)-2a detected in the H NMR of
the crude reaction mixture. It should be pointed out that
unexpectedly 4o has a syn relationship of chiral centers as
determined from the MPA ester.
The scope of the cascade reaction for aromatic thiolates was
examined next (Scheme 3). A remarkable inversion of
a
Scheme 3. Scope for the Reaction of Aryl Thiolates
a
b
Combined yield unless otherwise stated. Et2NH, toluene, 85 °C, 6
c
h (7c); Et2NH, MeOH, 40 °C, 2 h (8c). Combined yield for diols
(not shown). Overall isolated yield for anti-9 from 3a.
d
when benzyl sulfide 3b was submitted to the reaction
conditions compared with octyl sulfide 3a (from 90:10 to
77:23). Similarly to the anti diastereoisomers, syn aromatic
sulfides 4d and 4s (R = 4-MeO-C6H4) gave triols 8a and 8c in
good yields and with no loss of diastereoselectivity. Notably,
substrates 3m and 4s with an alkyl group at the double bond
(R1 = Bu) needed higher temperatures to undergo the [2,3]-
sigmatropic rearrangement. It should be pointed out that
diastereomeric triols anti-7 and syn-8 can be prepared at will
from the same sulfinyl diene by choosing the suitable thiolate.
The structure of the known triols 7a and 8a was further
confirmed by transformation to the isopropylidene ketals and
comparison of the NMR data14 allowing establishment of the
absolute configuration for the carbon−sulfide center in the
precursors (3a and 4d) which evolved through a suprafacial
sulfoxide-sulfenate rearrangement, transferring the chirality
from the C5−S bond to the new C3−O bond.1j,5a On the other
hand, imination of anti allylic sulfides 3a and 3b with
chloramine-T and subsequent [2,3]-sigmatropic rearrangement
of the transient sulfilimines (method B) gave a bis-hydroxy
sulfonamide derivative that was isolated as isopropylidene ketal
9 in moderate yield and with a small decrease in
diastereoselectivity from the starting materials.
Finally, diastereomerically enriched 1,4-hydroxy sulfides
anti-3q (87:13) and syn-4q (9:91) were protected as MOM
acetals (10 and 11) and treated with CH2I2/ZnEt2 in
oxygenated toluene to afford sulfide anti-12 or syn-13,
respectively, resulting from a [2,3]-sigmatropic rearrangement
of a sulfur ylide intermediate with excellent diastereoselectivity
and good isolated yields. It should be pointed out that both
sulfides are ultimately derived from a single starting diene
(E,Z)-2a (Scheme 5). The absolute configuration of 12 and 13
was further confirmed through selective removal of the MOM
protecting group (ZnBr2/C8H17SH/CH2Cl2/rt) to give
a
Conditions: The reaction was performed in toluene from 0 °C to rt
b
unless otherwise stated. The absolute configuration was determined
c
from the MPA esters 5 and 6 (see SI). Dr expressed as anti/syn ratio.
d
e
Combined yield. 20% of (E,E)- and (E,Z)-2a was detected as a
f
50:50 mixture. Monosilylation of 4d provides 4q in good yield (see
g
SI). 10% of (E,E)-2b was also observed in the 1H NMR of the crude
mixture.
diastereoselectivity was observed upon treatment of diene
(E,Z)-2a with sodium thiolates from thiophenol, thioanisole,
and 3,5-dichlorobenzenethiol leading mainly to syn-2-ene-1,4-
hydroxy sulfides 4c, 4d, and 4p. Lowering the reaction
temperature to −20 °C did not improve the diastereoselec-
tivity for 4c but led to lower conversion with partial double
bond isomerization to the less reactive (E,E)-2a. A similar
trend has been found for (E,Z)-dienes 2c and 2g to produce
syn 1,4-hydroxy sulfides (4r and 4s) in excellent yields and
selectivities. Sulfinyl dienes lacking a hydroxyl group (2d, 2e,
2f) gave sluggish reactions with aryl thiolates except for 2b
which selectively yielded 4q using the more polar solvent
DME. Interestingly, the addition of aromatic lithium thiolates
increases significantly the amount of anti 1,4-hydroxy sulfides
(3d and 3q), particularly for silyloxy diene 2b that produces
anti-3q with a complete reversal of diastereoselectivity
compared with sodium thiolate.
The diastereodivergent preparation of allylic sulfides 3 and 4
from sulfinyl dienes 2 allowed us to take advantage of the rich
reactivity of this moiety by stereocontrolled [2,3]-sigmatropic
rearrangements (Scheme 4). Initially, we examined the tandem
sulfide oxidation/sulfoxide-sulfenate reaction with m-CPBA
and Et2NH as a thiophile (method A) for anti hydroxy sulfides
3 that consistently led to triol derivatives 7a−7c maintaining
the anti/syn ratio of the starting materials (3a, 3f, and 3m).
Interestingly, a decrease in selectivity was observed for 7a
C
https://dx.doi.org/10.1021/acs.orglett.0c03929
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
pubs.acs.org/OrgLett
Letter
a
access to anti or syn acyclic triol and hydroxy sulfide derivatives
that can be obtained at will from a single 2-sulfinyl diene by the
proper choice of thiolate and counterion.
Scheme 5. Sulfur Ylide Rearrangement
ASSOCIATED CONTENT
* Supporting Information
■
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.0c03929.
Experimental details and chemical compound informa-
tion; copies of NMR spectra (PDF)
a
b
Combined yield. Isolated yield.
AUTHOR INFORMATION
Corresponding Author
■
hydroxy sulfides anti-14 and syn-15 (not shown) and
preparation of the MPA esters (see SI).
The simplified rationalization of the stereochemical outcome
of this tandem process shown in Scheme 6 results from a
Alma Viso − Instituto de Química Orgánica General, IQOG-
CSIC, 28006 Madrid, Spain; orcid.org/0000-0003-
2622-4777; Email: almaviso@iqog.csic.es
Authors
Scheme 6. Stereochemical Outcome for the Synthesis of 3
and 4
Marina Velado − Instituto de Química Orgánica General,
IQOG-CSIC, 28006 Madrid, Spain
́
Roberto Fernandez de la Pradilla − Instituto de Química
Orgánica General, IQOG-CSIC, 28006 Madrid, Spain;
orcid.org/0000-0002-6633-8499
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.0c03929
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
This research was supported by PID2019-107380GB-100 and
CTQ2016-77555-C2-2-R.
■
delicate interplay of factors such as starting material, thiol,
counterion, solvent, and temperature. We believe that initial
fast conjugate addition of alkyl thiolates onto the si-face of the
dienyl sulfoxide and stereoselective α protonation gives
transient allylic sulfoxide I that undergoes a favorable endo
[2,3]-sigmatropic rearrangement to sulfenate III, rapidly
cleaved by excess thiolate to produce anti-3. In contrast, the
use of aryl thiolates results in an enhanced syn selectivity that
may be attributed to β protonation of the intermediate sulfinyl
carbanion to produce allylic sulfoxide II, probably due to
stabilizing interactions between aromatic rings (p-Tol and ArS)
at the carbanion stage that bring about a conformational
change prior to protonation; this trend is particularly
important for sodium aryl thiolates. Subsequent exo [2,3]-
sigmatropic rearrangement produces sulfenate IV and
ultimately 2-ene-1,4-hydroxy sulfide syn-4 as the main product.
Interestingly, benzyl thiolates stand at an intermediate stage
consistently producing anti-3 with lower diastereoselectivities
than alkyl thiolates.
In summary, a diastereodivergent synthesis of anti and syn 2-
ene-1,4-hydroxy sulfides from enantiopure 2-sulfinyl dienes has
been described. The transformation entails a cascade reaction
triggered by a conjugate addition of thiolates to give a transient
allylic sulfoxide that undergoes sulfoxide-sulfenate rearrange-
ment followed by in situ sulfenate cleavage. The overall
diastereoselectivity is strongly influenced by the nature of
thiolate and counterion as well as by the structure of the
starting diene. We have also outlined that subsequent [2,3]-
sigmatropic rearrangements of these highly useful enantiopure
1,4-hydroxy sulfides provide an efficient and diastereoselective
REFERENCES
■
(1) For reviews on the sulfa-Michael addition, see: (a) Wadhwa, P.;
Kharbanda, A.; Sharma, A. Thia-Michael Addition: An Emerging
Strategy in Organic Synthesis. Asian J. Org. Chem. 2018, 7, 634−661.
́
(b) Nair, D. P.; Podgorski, M.; Chatani, S.; Gong, T.; Xi, W.; Fenoli,
C. R.; Bowman, C. N. The Thiol-Michael Addition Click Reaction: A
Powerful and Widely Used Tool in Materials Chemistry. Chem. Mater.
2014, 26, 724−744. (c) Chauhan, P.; Mahajan, S.; Enders, D.
Organocatalytic Carbon−Sulfur Bond-Forming Reactions. Chem. Rev.
2014, 114, 8807−8864. (d) Enders, D.; Luttgen, K.; Narine, A. A.
̈
Asymmetric Sulfa-Michael Additions. Synthesis 2007, 2007, 959−980.
For leading references: (e) Li, Y.-P.; Zhu, S.-F.; Zhou, Q.-L. Chiral
Spiro Phosphoramide-Catalyzed Sulfa-Michael Addition/Enantiose-
lective Protonation of Exocyclic Enones. Org. Lett. 2019, 21, 9391−
́
́
̌
̌
́
9395. (f) Ferko, B.; Zeman, M.; Formica, M.; Vesely, S.; Dohanosova,
J.; Moncol, J.; Olejníkova, P.; Berkes, D.; Jakubec, P.; Dixon, D. J.;
́
̌
́
Caletkova, O. Total Synthesis of Berkeleylactone A. J. Org. Chem.
̈
2019, 84, 7159−7165. (g) Rautschek, J.; Jager, A.; Metz, P. Formal
Synthesis of (−)-Codeine by Application of Temporary Thio
Derivatization. Org. Lett. 2018, 20, 832−835. (h) Fulton, J. L.;
Horwitz, M. A.; Bruske, E. L.; Johnson, J. S. Asymmetric
Organocatalytic Sulfa-Michael Addition to Enone Diesters. J. Org.
Chem. 2018, 83, 3385−3391. (i) Formica, M.; Sorin, G.; Farley, A. J.
M.; Díaz, J.; Paton, R. S.; Dixon, D. J. Bifunctional iminophosphorane
catalysed enantioselective sulfa-Michael addition of alkyl thiols to
alkenyl benzimidazoles. Chem. Sci. 2018, 9, 6969−6974. For a recent
review on the chemistry of organosulfur compounds, see: (j) Kaiser,
D.; Klose, I.; Oost, R.; Neuhaus, J.; Maulide, N. Bond-Forming and
-Breaking Reactions at Sulfur(IV): Sulfoxides, Sulfonium Salts, Sulfur
Ylides, and Sulfinate Salts. Chem. Rev. 2019, 119, 8701−8780.
D
https://dx.doi.org/10.1021/acs.orglett.0c03929
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
pubs.acs.org/OrgLett
Letter
(2) For sulfa-Michael additions to alkenyl sulfoxides, see: (a) De
Sulfinyl Dienes: The Preparation of Sulfinyl Iron(0) Dienes. J. Org.
Chem. 1997, 62, 6326−6343.
̈
Nicola, G. R.; Tatibouet, A.; Iori, R.; Rollin, P. Sulfur-containing
(8) Selected examples for the synthesis of 1,4-hydroxy sulfides:
(a) Chowhan, L.; Raghavan, S. Recent examples of the synthesis of
1,4-hydroxy sulfides Stereoselective synthesis of C3−C17 and C18−
C34 subunits of bullatanocin utilizing α-chloro sulfide intermediates.
Tetrahedron Lett. 2019, 60, 151132−151134 and previous papers
metabolites in radishes. Further exploration of glucoraphenin
desulfation. J. Sulfur Chem. 2013, 34, 48−54. (b) Gulea, M.;
Kwiatkowska, M.; Łyzwa, P.; Legay, R.; Gaumont, A.-C.;
́
Kiełbasinski, P. Michael addition to a chiral non-racemic 2-
phosphono-2,3-didehydrothiolane S-oxide. Tetrahedron: Asymmetry
2009, 20, 293−297. (c) Łyzwa, P.; Jankowiak, A.; Kwiatkowska, M.;
from this group. (b) Dormann, K. L.; Bruckner, R. Variable Synthesis
̈
of the Optically Active Thiotetronic Acid Antibiotics Thiolactomycin,
Thiotetromycin, and 834-B1. Angew. Chem., Int. Ed. 2007, 46, 1160−
1163.
́
Mikołajczyk, M.; Kiełbasinski, P.; Betz, A.; Jaffres, P.-A.; Gaumont, A.-
C.; Gulea, M. Diastereoselective Michael additions to α,β-unsaturated
α-sulfinyl phosphonates in the thiolane series. Tetrahedron Lett. 2007,
48, 351−355. (d) Usera, A. R.; Posner, G. H. Unexpected Steric
Effects of “Remote” Alkyl Groups on the Rate of Conjugate Additions
to Alkyl α,β-Ethylenic Sulfones, Sulfoxides, and Esters. J. Org. Chem.
2007, 72, 2329−2334. (e) Forristal, I.; Lawson, K.; Rayner, C.
Stereoselective conjugate addition of thiolate nucleophiles to (E)-γ-
hydroxy-α,β-unsaturated sulfoxides and sulfones. Sulfur Lett. 2003, 26,
89−94. (f) Mikołajczyk, M.; Midura, W. B. (+)-(S)-α-Diethoxyphos-
phorylvinyl p-Tolyl Sulfoxide: a New Chiral Michael Acceptor and
Dienophile. Tetrahedron: Asymmetry 1992, 3, 1515−1518. (g) Annun-
ziata, R.; Cinquini, M.; Colonna, S. Michael Additions to α,β-
Unsaturated Sulphoximides in Two-phase Systems. Kinetic Reso-
lution by Means of Chiral Phase-transfer Catalysts. J. Chem. Soc.,
Perkin Trans. 1 1980, 1, 2422−2424. (h) Tanikaga, R.; Sugihara, H.;
Tanaka, K.; Kaji, A. A Useful Route for Olefin Synthesis: Thermolysis
of the Michael Adducts of Aryl Vinyl Sulfoxides. Synthesis 1977, 1977,
299−301.
(9) (a) Raghavan, S.; Chiluveru, R. K.; Subramanian, S. G.
Stereoselective Formal Synthesis of (+)- and (−)-Cyclophellitol and
(−)-Conduritol-B and Synthesis of (−)-Conduramine-B Derivative
Using a Sulfinyl Moiety for C−O Bond Formation and α-Chloro
Sulfide for C−C Bond Formation. J. Org. Chem. 2016, 81, 4252−
4261. (b) Raghavan, S.; Kumar, V. V.; Chowhan, R. L. Highly
Stereoselective Preparation of Chiral α-Substituted Sulfides from α-
Chloro Sulfides via 1,2-Asymmetric Induction. Synlett 2010, 2010,
1807−1810.
(10) Kano, T.; Sakamoto, R.; Maruoka, K. Remote chirality control
based on the organocatalytic asymmetric Mannich reaction of α-thio
acetaldehydes. Chem. Commun. 2014, 50, 942−944.
(11) (a) Hartley, R. C.; Richards, I. C.; Warren, S. Stereocontrolled
synthesis of E-homoallylic sulfides with 1,4,5 related chiral centres
using the [2,3] sigmatropic rearrangement of sulfonium ylides. J.
Chem. Soc., Perkin Trans. 1 1996, 359−376. (b) Kosarych, Z.; Cohen,
T. A method for methylidenation and ethylidenation of an allylic
thioether leading to a 2,3-sigmatropic rearrangement. Failure of the
Simmons-Smith reaction in the presence of thioethers. Tetrahedron
Lett. 1982, 23, 3019−3022.
́
(3) (a) Colomer, I.; Gheewala, C.; Simal, C.; Velado, M.; Fernandez
de la Pradilla, R.; Viso, A. Sulfinyl-Mediated Stereoselective Overman
Rearrangements and Diels-Alder Cycloadditions. J. Org. Chem. 2016,
́
81, 4081−4097. (b) Fernandez de la Pradilla, R.; Urena, M.; Bates, R.
̃
(12) Northrop, B. H.; Frayne, S. H.; Choudhary, U. Thiol−
maleimide “click” chemistry: evaluating the influence of solvent,
initiator and thiol on the reaction mechanism, kinetics, and selectivity.
Polym. Chem. 2015, 6, 3415−3430.
(13) Similar behavior of this substrate was observed in the addition
of oxygen-centered nucleophiles; see ref 6c.
́
H.; del Aguila, M. A.; Colomer, I.; Viso, A. An Approach to the
Stereoselective Synthesis of Enantiopure Dihydropyrroles and
Aziridines from a Common Sulfinyl-Sulfinamide Intermediate. J.
Org. Chem. 2012, 77, 525−542.
́
́
(4) (a) Fernandez de la Pradilla, R.; Lwoff, N.; del Aguila, M. A.;
Tortosa, M.; Viso, A. [2,3]-Sigmatropic Rearrangements of 3-Sulfinyl
Dihydropyrans: Application to the Syntheses of the Cores of ent-
Dysiherbaine and Deoxymalayamicin A. J. Org. Chem. 2008, 73,
(14) (a) Evans, P.; Johnson, P.; Taylor, R. J. K. The Epoxy-
̈
Ramberg−Backlund Reaction (ERBR): A Sulfone-Based Method for
the Synthesis of Allylic Alcohols. Eur. J. Org. Chem. 2006, 2006,
1740−1754. (b) Denmark, S. E.; Chung, W. Lewis Base Activation of
Lewis Acids: Catalytic, Enantioselective Addition of Glycolate-
Derived Silyl Ketene Acetals to Aldehydes. J. Org. Chem. 2008, 73,
́
8929−8941. (b) Simal, C.; Bates, R. H.; Urena, M.; Gimenez, I.;
̃
́
Koutsou, C.; Infantes, L.; Fernandez de la Pradilla, R.; Viso, A.
Synthesis of Enantiopure 3-Hydroxypiperidines from Sulfinyl Dienyl
Amines by Diastereoselective Intramolecular Cyclization and [2,3]-
Sigmatropic Rearrangement. J. Org. Chem. 2015, 80, 7674−7692.
́
4582−4595. (c) Kuszmann, J.; Podanyi, B. Acetolysis of a 2,4-O-
benzylidene-L-ribo-hex-5-enitol derivative. Carbohydr. Res. 1994, 257,
217−226.
́
(5) (a) Colomer, I.; Velado, M.; Fernandez de la Pradilla, R.; Viso,
A. From Allylic Sulfoxides to Allylic Sulfenates: Fifty Years of a Never-
Ending [2,3]-Sigmatropic Rearrangement. Chem. Rev. 2017, 117,
14201−14243. (b) Reggelin, M. [2,3]-Sigmatropic Rearrangements of
Allylic Sulfur Compounds. Top. Curr. Chem. 2007, 275, 1−65.
(c) Walker, J. R.; Merit, J. E.; Thomas-Tran, R.; Tang, D. T. Y.; Du
Bois, J. Divergent Synthesis of Natural Derivatives of (+)-Saxitoxin
Including 11-Saxitoxinethanoic Acid. Angew. Chem., Int. Ed. 2019, 58,
1689−1693. (d) Nyalata, S.; Raghavan, S. Convergent Stereoselective
Synthesis of the C16−C37 Subunit of Sorangicin A. Org. Lett. 2019,
21, 7778−7781.
́
(6) (a) Fernandez de la Pradilla, R.; Colomer, I.; Urena, M.; Viso, A.
̃
Enantiopure 1,4-Diols and 1,4-Aminoalcohols via Stereoselective
Acyclic Sulfoxide-Sulfenate Rearrangement. Org. Lett. 2011, 13,
́
̃
2468−2471. (b) Colomer, I.; Urena, M.; Viso, A.; Fernandez de la
Pradilla, R. Sulfinyl-Mediated Stereoselective Functionalization of
Acyclic Conjugated Dienes. Chem. - Eur. J. 2020, 26, 4620−4632.
́
(c) Fernandez de la Pradilla, R.; Velado, M.; Colomer, I.; Simal, C.;
Viso, A.; Gornitzka, H.; Hemmert, C. Remote Stereocontrol in the
Synthesis of Acyclic 1,4-Diols and 1,4-Aminoalcohols from 2-Sulfinyl
Dienes. Org. Lett. 2014, 16, 5200−5203.
(7) Paley, R. S.; de Dios, A.; Estroff, L. A.; Lafontaine, J. A.;
Montero, C.; McCulley, D. J.; Rubio, M. B.; Ventura, M. P.; Weers, H.
́
L.; Fernandez de la Pradilla, R.; Castro, S.; Dorado, R.; Morente, M.
Synthesis and Diastereoselective Complexation of Enantiopure
E
https://dx.doi.org/10.1021/acs.orglett.0c03929
Org. Lett. XXXX, XXX, XXX−XXX