Ejoc 202200441

Research Article
doi.org/10.1002/ejoc.202200441
www.eurjoc.org
Molecular Iodine Mediated Oxidation of Arylated α-

Carbonyl Sulfoxonium Ylides to 1,2-Dicarbonyl-Containing
Compounds
Radell Echemendía,[a] Matheus P. De Jesus,[a] Lucas G. Furniel,[a] David Philip Day,[a] and
Antonio C. B. Burtoloso*[a]
Sulfoxonium ylides in recent years have proved to be versatile reactants. Furthermore, the protocol benefits from the use of
building blocks and have found applications in the synthesis of inexpensive molecular iodine to mediate the oxidation and,
structurally diverse organic molecules. In this work, we report a from a sustainability viewpoint, short reaction times (30
new oxidative, molecular iodine-mediated transformation on minutes), ambient temperature, and ethyl acetate as a greener
sterically encumbered arylated sulfoxonium ylides, which give reaction solvent. Experimental studies also gave insight to the
access to 1,2-dicarbonyl containing compounds. Twenty-six mechanism of the reaction, involving DMSO as an oxygen
examples have been realized (47–92 % yields), with structural source.
diversity modified at two key sites on the sulfoxonium ylide
Introduction
The 1,2-dicarbonyl motif can be mapped onto numerous

natural products or organic compounds featured in drug
discovery programs (Figure 1), showcasing key biological
activities including antimicrobial,[1] antifungal activities,[2] or
alternatively acting as acetylcholine receptor modulators[3] and
also as kinase inhibitors.[4]
Within the literature, a broad variety of classical methods to
generate 1,2-dicarbonyl containing compounds using oxida-
tion-derived reaction conditions is well defined.[5] Many of these
processes give rise to either 1,2-diketone[6] or 1,2-ketoester[7]
products, and benefit from using simple (and/or commercially)
available reactants (such as alkynes, alkenes, alcohols),[8] utilize
cheap oxidation sources (air[9]) and possibly incorporate green
or renewable protocols such as sustainable solvents[10] (Sche- Figure 1. Biologically relevant 1,2-dicarbonyl containing natural products
me 1a). In our laboratory, we have recently focused on and medicinal compounds.
developing new transformations of sulfoxonium ylide substrates
to access intricate, high-value products,[11] and we postulated
that sulfoxonium ylides could pose as suitable reactants to
access 1,2-dicarbonyl containing products (Scheme 1b). predicted and accessed. Subsequently, we have found new
In 2017, our group reported that ketosulfoxonium ylides applications of alternative sulfoxonium ylides,[13] many of which
react with halogen sources to afford α,α-haloketones,[12] and have much different reactivities, for example arylated ketosul-
depending on substrate type, halide source (or alkyl halide foxonium ylides and sulfoxonium esters[14] – in this article, we
reactant used), a variety of interesting products can be report a new oxidative process mediated by molecular iodine[15]
that smoothly converts prochiral, sterically crowded ketosul-
foxonium ylides or sulfoxonium ester ylides into a library of 1,2-
[a] Dr. R. Echemendía, M. P. De Jesus, L. G. Furniel, Dr. D. P. Day, dicarbonyl containing products (Scheme 1b). This newly devel-
Prof. Dr. A. C. B. Burtoloso
Chemistry Institute at São Carlos,
oped protocol is time efficient, employs an inexpensive
University of São Paulo, oxidative reagent, allows modification at two key sites of the
13560-970, São Carlos, SP, Brazil prochiral sulfoxonium ylides to access 1,2-dicarbonyl com-
E-mail: antonio@iqsc.usp.br
pounds. Moreover, mechanistic experimental studies indicate
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/ejoc.202200441 that the oxygen source to reach these products come from
Part of the “Organic and Supramolecular Chemistry in Latin America” Spe- dimethyl sulfoxide, that is released after the first step.
cial Collection.
Eur. J. Org. Chem. 2022, e202200441 (1 of 7) © 2022 Wiley-VCH GmbH

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Research Article
doi.org/10.1002/ejoc.202200441
Scheme 1. a) Generic routes highlighting known reactants used to access

1,2-dicarbonyl compounds. b) This work: transformation of arylated α-
carbonyl sulfoxonium ylides into 1,2-dicarbonyl compounds.
Table 1. Optimization of reaction conditions.
Entry Halogen Source[a] Time Solvent Yield 5 a[b,c]
1 Selectfluor 60 min MeCN 22

2 Iodine 60 min MeCN 57
3 NIS 60 min MeCN 28
4 NBS 60 min MeCN 11
5 Iodine 60 min THF 56
6 Iodine 60 min Dioxane 35
7 Iodine 60 min DCM 40
8 Iodine 60 min DMF 38
9 Iodine 60 min EtOAc 70
10 Iodine 30 min EtOAc 74
11 Iodined 30 min EtOAc 69
12 Iodinee 30 min EtOAc 17
13 Iodine 30 min DMSO 72
[a] Reaction was performed using 2 a (0.10 mmol), halogen source

(0.10 mmol) and solvent 1 mL [0.1 M]. [b] Determined after flash column
chromatography purification. [c] When Iodine was used as halogen source,
after completing the reaction, the mixture was washed with sodium
thiosulfate, and the organic phase was separated and purified by flash
column chromatography purification. [d] Reaction was performed using
4 Å molecular sieves (powder). [e] Reaction was performed using catalytic
amount of I2 (20 mol%).
Scheme 2. Accessing prochiral sulfoxonium ylides via method a) Rhodium
catalysis or b) Palladium catalysis. Reaction conditions: method a) diazoester
(1 equiv.), DMSO, or method b) ketosulfoxonium ylide (1 equiv.), aryl
bromide (1.5 equiv.), MeCN.
Results and Discussion
To begin our studies, we utilized two approaches to generate a

library of arylated sulfoxonium ylides (Scheme 2). In line with Under both metal-catalyzed approaches, variation to both
our previously reported literature conditions,[16] either rhodium the ester moiety and the α-aryl moiety was well tolerated, and
catalyzed dimethylsulfoxide insertion into diazonium esters 1 a– in total, twenty-six arylated sulfoxonium ylides were accessed in
f gave access to sulfoxonium ylides 2 a–f (Method A, Scheme 2), yields ranging between 20–92 %. With a library of reactants 2 a–
or alternatively palladium catalyzed C H activation of sulfoxo- z in hand for our oxidation reaction to access 1,2-dicarbonyl
nium ylides 3 a–i reacting with aryl-bromides 4 a–k to yield products, we firstly investigated the optimization of this
sulfoxonium ylides 2 g–z (Method B, Scheme 2). oxidation reaction (Table 1). Utilizing sulfoxonium ylide 2 a as

Research Article
doi.org/10.1002/ejoc.202200441
Scheme 3. Exploring substrate scope for this transformation.
test substrate, we began by screening a range of halogenating catalytic amounts (20 mol%, entry 12) gave a detrimental effect
agents that afforded 1,2-dicarbonyl product methyl 2-oxo-2- on isolated reaction yield.
phenylacetate 5 a (entries 1–4, Table 1). Selectfluor, N-iodosucci- To further explore the scope of this transformation, we next
nimide and N-bromosuccinimide all mediated the transforma- utilized arylated sulfoxonium ylides 2 b–2 z as reactants to
tion albeit in low yields. We were happy to observe that when access 1,2-dicarbonyl products 5 b–z (Scheme 3). Modification
molecular iodine was chosen as reactant (entry 2), product 5 a of the ester moiety was initially trialed – incorporation of
was accessed in an improved 57 % yield. Moving our attention methyl (5 a, 74 %), ethyl (5 e, 61 %), t-butyl (5 q, 81 %), phenoxy
to further enhancing the process, we next tested reaction (5 r, 91 %), diphenylmethanol (5 b, 80 %) and 2,2,2-trichloroe-
solvents – THF, dioxane, DCM, DMF (entries 5–8), all of which than-1-ol (5 c, 75 %) were all tolerated under the reaction
offered no yield improvements to that observed in entry 2 in conditions. Furthermore, expanding the scope to keto-derived
which acetonitrile was employed as solvent. Pleasingly, ethyl 1,2-dicarbonyl products 5 t-x could also be realized by utilizing
acetate as reaction solvent gave a further boost in yield (70 %, ketosulfoxonium ylides 2 t–x – good yields with these examples
entry 9), and shortening the reaction time from 60 min to were observed where R1 was a substituted aryl, and interest-
30 min gave our optimum reaction conditions (74 % yield of 5 a, ingly replacing R1 for a t-butyl substituent led to maintaining
entry 10). The addition of molecular sieves did not hinder, nor product yield of 5 u (80 %).
aid the process (entry 11), and employing molecular iodine in With the keto and ester functionalities at R1 investigated, we
next turned our attention towards substitutions onto the aryl

Research Article
doi.org/10.1002/ejoc.202200441
Figure 2. 1H NMR studies at different reaction times.
ring systems observed at the α-position on the arylated Scheme 4) on the dicarbonyl compounds 5. According to
sulfoxonium ylides. In these examples, the R1 substituent was literature[17], participation of DMSO as an oxygen source in
maintained as a methoxy ester substituent. Some of the highest similar systems, instead of water or molecular oxygen, is most
yields observed in this transformation occurred when alkyl probably and seems to be the major path to give compound 5.
substituents were found at R2, possibly allowing inductive To rule-out the intermediacy of water and molecular oxygen, a
effects to aid the oxidation of the carbon atom to which the set of experiments were performed. The reaction of 2 a and I2
sulfoxide moiety is attached to (see examples 5 g–i, 84–92 % under inert atmosphere (argon) provided 5 a in 72 % yield.
yield). Arguably a correlation was observed on the installation Furthermore, the use of dry ethyl acetate, or its combination
of an electron withdrawing moiety on the aryl ring at the para with molecular sieves, in the reaction vessel gave compound
position and a slight loss in reaction yield; Presumably, due to 5 a in 70 % yield (Scheme 4A). Performing the reaction on the
the deactivation of the nucleophilic nature of the sulfoxonium NMR tube using CDCl3 also revealed the formation of com-
carbon atom (see entries 5 k, 5 l, 5 o, 5 v–z, with yields ranging pound 5 a (and total consumption of 2 a after 30 min). This
between 49–58 %) or non-stabilization of a possible carbocation result showed formation of the product before the aqueous
intermediate (see discussion in Scheme 4B). Halides were also work-up in our optimized conditions. In time NMR also provided
well incorporated (entries 5 j and 5 p), the latter example also interesting insights to corroborate the participation of the
showing tolerance of incorporating a substituent at the ortho released DMSO as the oxygen source (see Scheme 4b), but also
position on the aryl ring system. Attempts to replace the aryl by indicated a minor path involving the formation of the unstable
an alkyl group in the ylides 2 proved to be fruitless in providing diiodide 6, that may give product 5 after aqueous work-up.
the 1,2 dicarbonyl derivative, under the optimized reaction Initially, it was observed the quick formation of DMSO, detected
conditions. by the residual peak at 2.62 ppm (CDCl3).[18] Interestingly, after
To finalize our studies, we decided to investigate the 30 minutes of reaction, a peculiar singlet at 2.32 ppm was
mechanism of the reaction. One of the main questions is the observed, which presumably indicated the formation of
source of oxygen atom (colored in blue; see Figure 2 and iododimethyl sulfonium iodine.[19] This was later confirmed by

Research Article
doi.org/10.1002/ejoc.202200441
Scheme 4. Mechanistic proposal for the molecular iodine oxidation of arylated sulfoxonium ylides.
the preparation of the corresponding salt. Moreover, a small to provide the formation of intermediate B (A also react with
singlet in 3.91 ppm, indicated that diiodide 6 is also being iodide anion to give diiodide 6 as a minor path). Intermediate B
formed in the reactions conditions and probably is being is collapsed with iodide to give 5 a and NMR detected sulfonium
converted to product 5 a in the aqueous work-up (reaction of salt (iododimethyl sulfonium iodine). Diiodide 6 is converted to
diazo compound 1 a with iodine in NMR tube, in dry CDCl3, 5 a during aqueous work-up.
showed an intense singlet at 3.91 ppm + the hydrogen signals
of the aromatic ring; the reaction of similar diazo compounds
and bromine, in DCM, is described in the literature20 to furnish Conclusion
the respective dibromide). Interestingly, rapid IR analysis of the
crude diiodide revealed just one carbonyl in the first seconds, Our approach towards accessing decorated 1,2-dicarbonyl
but the appearance of a second one with time. This indicates compounds has been realized from prochiral sulfoxonium ylides
that iodide 6 is unstable and is probably being converted to the for the first time utilizing molecular iodine as oxidant whilst
dicarbonyl derivative in the air moisture during IR acquisition. employing mild and sustainable reaction conditions. The
Based on the results discussed above, a possible mechanism method provides facile access to important scaffolds that can
for this transformation was proposed (Scheme 4B), with a major be mapped onto known, biologically relevant natural products
and minor path to give 5 a. The initial step of the reaction and drug candidates, and as such gives chemists an extra
would involve a nucleophilic attack of the sulfoxonium ylide to approach to access this important class of organic products. In
the electrophilic molecular iodine, followed by the extrusion of addition, the method developed utilizes ethyl acetate as a
DMSO and the formation of a α-carbonyl benzylic carbocation green reaction solvent, and benefits from being conducted at
A[21] (the fact that α-alkyl sulfoxonium ylides did not furnish any room temperature under short reaction times. We envisage the
product corroborates that a carbocation may be involved; see future growth and applications of sulfoxonium ylide chemistry
Scheme 4C). The intermediate A then reacts with the sulfoxide to provide new and important contributions to the field of

Research Article
doi.org/10.1002/ejoc.202200441
organic chemistry in years to come, especially due to their rinsing. After evaporation of all volatiles, purification by flash
stability, ease of synthesis, interesting reactivities and novel chromatography using AcOEt/hexanes as eluent (50 % 100 %).
transformations that have yet to be discovered. Representative procedure for iodine oxidation of α-aryl sub-
stituted sulfoxonium ylides: To a 4 mL reaction vial with a Teflon
coated septum screw-top was added 0.1 mmol of sulfoxonium ylide
Experimental Section (1.0 equiv.), 0.1 mmol of iodine (1.0 equiv.) and 1 mL of AcOEt
(0.1 M). The reaction was stirred at room temperature for thirty
General information. The TLC analyses were performed using silica minutes. Next, the reaction mixture was washed with a saturated
gel plates, with detection by UV-absorption (254 nm) for visual- solution of sodium thiosulfate (4 × 1 mL). The organic phase was
ization. Flash column chromatography was performed using silica concentrated under reduced pressure to furnish the crude product
gel 200–400 Mesh or using Biotage IsoleraTM Prime (Snap Ultra that was purified by flash chromatography using Biotage IsoleraTM
10 g). All NMR analyses were recorded using CDCl3 as solvent and Prime (Snap Ultra 10 g).
TMS as internal standard (1H NMR were recorded at 500 MHz and
13
C{1H} NMR at 125 MHz using 500 (Agilent Technologies - 500/54
Premium Shielded) instruments. Chemical shifts are reported in
ppm downfield from TMS with reference to internal solvent. 1H Acknowledgements
NMR multiplicities are reported as follows: s = singlet; d = doublet;
t = triplet; q = quartet; m = multiplet. Infrared spectra were obtained We would like to thank São Paulo Research Foundation (FAPESP)
using FT-IR (Bruker, model ALPHA) at 4.0 cm-1 resolution and are for fellowship grants to RE (2019/12300-5), MPJ (2020/07143-5),
reported in wave-numbers. The samples were dispersed neat on a
LGF (2018/17800-3) and DPD (2019/05002-8), and for financial
ZnSe crystal (ATR mode). High-resolution mass spectra (HRMS) were
recorded using a MALDI-TOF/TOF AutoflexMax Bruker Daltonics. support (2020/07147-0) to A. C. B. B. We also thank National
Reaction setup: Air- and moisture-sensitive reactions were con- Council for Scientific and Technological Development (CNPq) for
ducted in flame- or oven-dried glassware equipped with tightly fellowship grant 140614/2020-6.
fitted rubber septa and under a positive pressure of dry nitrogen.
Reagents and solvents were handled by using standard syringe
techniques. Unless stated otherwise, all the yields refer to isolated
products after flash column chromatography. Melting Points: All
Conflict of Interest
melting points were measured Barnstead Electrotherm 1001D/1001
Mel-Temp Capillary Melting Point apparatus and are uncorrected. The authors declare no conflict of interest.
Solvents/chemicals: Ethyl acetate, hexanes, methanol, and chloro-
form were used as received. Acetonitrile and dimethyl sulfoxide
were dried over 4 Å molecular sieves prior to use. All other reagents Data Availability Statement
were used directly as received from the manufacturer.
The data that support the findings of this study are available in
General procedures for preparation of α-aryl substituted the supplementary material of this article.
sulfoxonium ylides
General procedure A: In a 50 mL round bottomed flask were added Keywords: Dicarbonyl compounds · Iodine · Oxydation ·
Rh2(OAc)4 (4.4 mg, 0.09 mmol, 1 mol %) and dry DMSO (5 mL). The Sulfoxonium ylides · Sulfur ylides
system was closed, placed under argon atmosphere and heated to
70 °C in oil bath. To this solution, was slowly added a solution of
the corresponding 2-diazo-2-phenylester (1.5 mmol, 1.0 eq) in dry
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Research Article

Molecular Iodine Mediated Oxidation of Arylated α-

The 1,2-dicarbonyl motif can be mapped onto numerous

Eur. J. Org. Chem. 2022, e202200441 (1 of 7) © 2022 Wiley-VCH GmbH

Scheme 1. a) Generic routes highlighting known reactants used to access

Table 1. Optimization of reaction conditions.

Entry Halogen Source[a] Time Solvent Yield 5 a[b,c]

1 Selectfluor 60 min MeCN 22

[a] Reaction was performed using 2 a (0.10 mmol), halogen source

To begin our studies, we utilized two approaches to generate a

Eur. J. Org. Chem. 2022, e202200441 (2 of 7) © 2022 Wiley-VCH GmbH

Scheme 3. Exploring substrate scope for this transformation.

Eur. J. Org. Chem. 2022, e202200441 (3 of 7) © 2022 Wiley-VCH GmbH

Figure 2. 1H NMR studies at different reaction times.

Eur. J. Org. Chem. 2022, e202200441 (4 of 7) © 2022 Wiley-VCH GmbH

Eur. J. Org. Chem. 2022, e202200441 (5 of 7) © 2022 Wiley-VCH GmbH

Eur. J. Org. Chem. 2022, e202200441 (6 of 7) © 2022 Wiley-VCH GmbH

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