Iron (III) chloride-catalyzed direct sulfonylation of alcohols with sodium arenesulfinates

Article abstract of DOI:10.1002/adsc.200900905

A new protocol for the direct sulfonylation of benzylic, allylic and homoallylic alcohols with sodium arenesulfinates is described by using iron (III) chloride as a catalyst and chlorotrimethylsilane as an additive. This method requires no preactivation o

Full text of DOI:10.1002/adsc.200900905

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DOI: 10.1002/adsc.200900905
Iron(III) Chloride-Catalyzed Direct Sulfonylation of Alcohols
G
with Sodium Arenesulfinates
M. Amarnath Reddy,a P. Surendra Reddy,a and B. Sreedhara,*
a
Indian Institute of Chemical Technology (Council for Scientific and Industrial Research), Hyderabad – 500007, India
Fax : (+91)-40-2716-0921; phone: (+91)-40-2719-1715; e-mail: sreedharb@iict.res.in
Received: December 29, 2009; Revised: June 18, 2010; Published online: August 16, 2010
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/adsc.200900905.
Abstract: A new protocol for the direct sulfonyla-
tion of benzylic, allylic and homoallylic alcohols
with sodium arenesulfinates is described by using
hydroxy group in alcohols by sulfinate salts through
nucleophilic substitution is generally difficult because
of the inefficient leaving group ability of the hydroxy
group which generally requires preactivation by trans-
forming it into a good leaving group such as halide or
mesylate.[8] Recently, the direct sulfonation of benzyl
carbamates and allylic alcohols using palladium cata-
lysts has been developed.[9] Although the above meth-
ods are encouraging, they require expensive phos-
phine ligands to promote the reaction which is unde-
sirable because of their toxicity and sensitivity to air
as well as moisture. Very recently Tian et al. reported
a convenient protocol for the synthesis of benzylic
and allylic sulfones through the reaction of alcohols
with sulfinyl chlorides as well as alkylation reaction of
ironACHTUNGTRENNUNG(III) chloride as a catalyst and chlorotrimethyl-
silane as an additive. This method requires no pre-
activation of alcohols. Surprisingly in the reaction
with homoallyl alcohols nucleophilic addition of
sulfinate anion, occurs at the terminal double bond
instead of nucleophic substitution at the alcohol.
Keywords: benzylic alcohols; chlorotrimethylsilane;
direct sulfonylation; homoallylic alcohols; sodium
p-toluenesulfinate
sulfinic acids with sulfonamides via sp3 C N bond
À
cleavage.[10]
The sulfonyl group is a well-established activating
Thus, in view of the demand for efficient, economic
moiety that is introduced into an intermediate mole- and ecologically valuable processes, the direct sulfo-
À
cule for the construction of C C bonds and other nylation of alcohols with suitable salts without any
transformations.[1] The ability of the sulfonyl group to stoichiometric hydroxy group activators would be an
stabilize carbanions is one of the best known features environmentally benign protocol. Since the pioneer-
of these compounds[2] and they also act as radical sta- ing work of Tamura and Kochi,[11] iron salts have
bilizers[3] and cationic synthons.[4] Aryl alkyl sulfones emerged as alternative and promising catalysts for
have become a popular tool for the synthesis of vari- many organic transformations,[12] such as oxidation,[13]
ous natural products as the a-carbanion is readily hydrogenation,[14] hydrosilylation,[15] rearrangement,[16]
generated by reaction with a base and reacts with var- Michael addition,[17] carbon-carbon[18] and carbon-het-
ious electrophiles such as alkyl halides and alde- eroatom bond-forming reactions;[19] also the oxidative
hydes.[5] The allyl phenyl sulfones are also excellent coupling of arynes[20] has been extensively studied. In
sources for regio- and diasterioselective diene synthe- addition to that, various iron-catalyzed cross-coupling
sis via Julia olefination procedure.[6] In this context, reactions
including
Sonogashira,[21]
Heck,[22]
the direct sulfonylation of alcohols would be quite an Kumada,[23] Negishi,[24] and Suzuki[25] reactions have
important process to provide useful building blocks in been developed. Moreover, iron salts have been suc-
organic synthesis. Earlier attempts to carry out the cessfully employed for the activation of alcohols to-
direct sulfonylation of alcohols were made using wards various nucleophiles.[26]
Brønsted acids such as AcOH, HCOOH and HCl to
We have recently developed a highly efficient
afford aryl alkyl sulfones.[7] However, in terms of method for the b-sulfonation of a,b-enones using
functional group tolerance, side reactions, and the re- FeCl3/TMSCl as catalytic system.[27] As our previous
action conditions, most of these reagents may have research focused on the direct nucleophilic substitu-
one or more drawbacks. The direct sulfonylation of a tion of alcohols,[28] with regard to the importance of
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Table 1. Optimization of reaction conditions for the direct sulfonylation.[a]
[a]
[b]
Reaction conditions: benzhydrol (1 mmol), sodium p-toluenesulfinate (1.2 mmol),
catalyst (15 mol%), additive (1.2 equiv.), solvent (3 mL), 458C.
Yield after column chromatography.
sulfones as intermediates in organic synthesis, in the temperature. Obviously, TMSCl proved to be the best
present work, we report our investigations on the ap- additive, while other additives disfavored the reaction
plication of FeCl3 as catalyst with TMSCl as an addi- to different degrees (Table 1, entries 11 and 12). A
tive for the practical and atom economic synthesis of control experiment with FeCl3 in the absence of
aryl alkyl sulfones through direct sulfonylation of TMSCl was ineffective and no product was obtained,
benzyl, allylic and homoallylic alcohols. In our initial whereas TMSCl alone gave the desired product in
studies, various iron catalysts in combination with dif- 37% yield (Table 1, entries 13 and 14). Noteworthy is
ferent solvents were investigated using benzhydrol that TMSCl not only generates nucleophilic the sulfi-
and sodium p-toulenesulfinate as model substrates nate anion from its salts but also activates the alcohol
(Table 1). The reaction conditions were optimized and with its Lewis acidity.[29] However, only a trace
the best conditions were found to be 15 mol% FeCl3 amount of the product was obtained with TMSOTf al-
and 1.2 equiv. of TMSCl as shown in Table 1, entry 1. though it is more Lewis acidic, which suggests that
By virtue of these optimized conditions, the reaction the activity does not necessarily depend on the Lewis
afforded the desired product in 96% yield. Reactions acidity of the silicon source (Table 1, entry 15).
with other iron catalysts such as FeCl2, Fe
G
Subsequently, on the basis of the optimized reac-
FeSO4, Fe2O3 did not generate the desired product in tion conditions, the scope of this FeCl3-catalyzed
appreciable yields (Table 1, entries 2–5). However, direct sulfonylation of several structurally diverse
the reaction with Fe(0) gave the product in moderate benzylic alcohols with sodium p-toluenesulfinate was
yield (Table 1, entry 6). Subsequently, the reaction explored and the results are summarized in Table 2.
conditions were optimized by employing different sol- In general, the reaction proceeded efficiently with
vents, wherein various polar and non-polar solvents various benzylic alcohols and gave the products in
were examined and it was found that all of them had good to excellent yields. Benzhydrols with both elec-
a negative influence on the reaction to different de- tron-donating or electron-withdrawing groups under-
grees (Table 1, entries 7–10).
went the desired reaction and gave the products[30] in
Having gained some crucial insights into the effect excellent yields. Other secondary benzylic alcohols
of different catalysts, further optimization was per- (Table 2, entries 4–8) also underwent the reaction
formed on exploring the effect of additives as well as smoothly to give the desired products in good to ex-
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IronACHTUNGTRENNUNG(III) Chloride-Catalyzed Direct Sulfonylation of Alcohols with Sodium Arenesulfinates
Table 2. Direct sulfonylation of different secondary alcohols with sodium p-toluene-
sulfinate salt using FeCl3 and TMSCl.[a]
[a]
Reaction conditions: alcohols (1 mmol), sodium p-toluenesulfinate (1.2 mmol),
FeCl3 (15 mol%), TMSCl (1.2 mmol), dichloromethame (3 mL), 458C.
Yield after column chromatography.
[b]
cellent yields, which can be attributed to the forma- ic alcohols and gave the expected sulfonyl ethers in
tion of a more stabilized carbocation intermediate.[31] good yield (Table 2, entries 9 and 10).
The formed products were useful for the synthesis of
The present catalytic system was also found to be
tri- and tetrasubstituted olefins.[5d] The reaction was suitable for the direct sulfonylation of non-benzylic
equally effective for the sulfonylation of cyclic benzyl- alcohols, such as cyclohexanol and 4-tert-butylcyclo-
hexanol and the respective products obtained in good
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Table 3. Direct sulfonylation of different benzyl alcohols with sodium p-toluene-
sulfinate salt using FeCl3 and TMSCl.[a]
[a]
Reaction conditions: alcohols (1 mmol), sodium p-toluenesulfinate (1.2 mmol),
FeCl3 (15 mol%), TMSCl (1.2 mmol), dichloromethane (3 mL) at 458C.
Yield after column chromatography average on 3 runs.
[b]
yields (Table 2, entries 10 and 11). However, the reac- in moderate yields. However, only a trace amount of
tions with butanol, isopropyl alcohol and tert-butyl al- the product was formed with p-nitrobenzyl alcohol
cohol were not successful.
which may be attributed to the generated cation that
With these encouraging results in hand, we subse- is influenced by the electronic and steric factors of
quently set out to explore the scope of various benzyl benzylic alcohols and the formed cation may be un-
alcohols and the results are listed in Table 3. In this stable.
study different substituted benzyl alcohols were trans-
In further experiments, with regard to the impor-
formed into their corresponding benzyl aryl sulfones tance of allylic sulfones,[32] we investigated the sulfo-
Table 4. Direct sulfonylation of different allyl alcohols with sodium p-toluenesulfinate
salt using FeCl3 and TMSCl.[a]
[a]
All reactions were performed on a 1.0 mmol scale in the presence of 15 mol% FeCl3,
1.2 equiv. of TMSCl in Dichloromethane at 458C.
Yields are the average of 3 runs.
[b]
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IronACHTUNGTRENNUNG(III) Chloride-Catalyzed Direct Sulfonylation of Alcohols with Sodium Arenesulfinates
Table 5. Direct sulfonylation of different homoallyl alcohols with sodium p-toluenesulfinate
salt using FeCl3 and TMSCl.[a]
[a]
All reactions were performed on a 1.0 mmol scale in the presence of 15 mol% of FeCl3,
1.2 equiv. of TMSCl in dichloromethane at 458C.
Yields are the average of 3 runs after column chromatography.
[b]
nylation of four different allylic alcohols which sulting in the formation of allylic sulfones instead of
showed similar reactivity as benzhydrols and the de- homoallylic sulfones with double bond migration.
sired products were obtained in good yields (Table 4).
To the best of our knowledge, this represents the
In the case of cinnamyl alcohol, the product was ob- first example of an FeCl3-catalyzed addition of sulfi-
tained in moderate yield along with some unidentified nate anion to the unactivated double bond. Also, this
by-products (Table 4, entry 2).
reaction broadens the scope of Li et al.ꢁs work on the
During our investigation of the FeCl3-catalyzed isomerization of the double bond that occurs with
direct sulfonylation of homoallylic alcohols (Table 5), ruthenium catalysts in water.[33] To further evaluate
we were surprised to find that nucleophilic addition the scope of this reaction, different homoallylic alco-
of sulfinate anion occurs at the terminal double bond hol derivatives were subjected to the optimized reac-
instead of nucleophic substitution at the alcohol, re- tion conditions and the results are shown in Table 5.
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Table 6. Direct sulfonylation of benzhydrol with different
the reaction with simple homoallylic alcohols afforded
allylic and homoallylic sulfones in 10% yield as insep-
arable mixtures in the ratio of 1:1.[34]
sulfinate sodium salts.[a]
Furthermore, the scope of the reaction with respect
to sulfinate sodium salt substrate was also examined
and the results are given in Table 6. Both electron-do-
nating as well as electron-withdrawing substituents
gave the corresponding sulfonyl ethers were obtained
in good yields within 12 h (entries 1–3).
When the optically active (R)-1-(naphthalen-2-yl)-
AHCTUNGTREGeNNUN thanol, which was prepared by the oxazaborolidine-
catalyzed asymmetric borane reduction of the 1-
(naphthalen-2-yl)ethanone, reacted with sodium p-tol-
uenesulfinate salt, only the racemic product was ob-
tained (Scheme 1). This suggests a reaction mecha-
nism in which a carbenium intermediate is formed.
To get an insight into the mechanism, we per-
formed several experiments to confirm the possibili-
ties of the best reaction system. Scheme 2 shows pos-
[a]
All reactions were performed on a 1.0 mmol scale in the
presence of 1.2 equiv. of sulfinate sodium salt, 1.2 equiv
of TMSCl in dichloromethane at 458C.
Yields after column chromatography.
[b]
With bromo- or methyl-substitution at the para posi- sible pathways for the FeCl3-catalyzed sulfonylation
tion or without any substitution on the phenyl ring, reaction using TMSCl as an additive. In this reaction,
the allylic sulfones were obtained in good yields along TMSCl plays a crucial role by dual activation of both
with trace amounts of homoallylic sulfones (entries 1– alcohol and sodium p-toluenesulfinate. First it reacts
3). On the other hand, with 2,6-dibromo-4-(1- with an alcohol to give trimethylsilyl ether I of an al-
hydroxyACHTUNGTRENNUNGbut-3-enyl)phenol we observed the formation cohol and generates HCl, which can convert an alco-
of homoallylic sulfones along with trace amounts of hol or its TMS ether to a dimeric ether II. It is also
allylic sulfones (Table 5, entry 4). On the other hand, known that with a catalytic amount of Lewis acids,
Scheme 1. Direct sulfonylation of an optically active alcohol with sodium p-toluenesulfinate salt.
Scheme 2. Proposed mechanism for the direct sulfonylation of alcohols with sulfinate sodium salts using FeCl3 and TMSCl.
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IronACHTUNGTRENNUNG(III) Chloride-Catalyzed Direct Sulfonylation of Alcohols with Sodium Arenesulfinates
Scheme 3. Proposed mechanism for the direct sulfonylation of homoallylic alcohols with sodium p-toluenesulfinate using
FeCl3 and TMSCl
benzylic and allylic alcohols rapidly convert into di- tion of sulfinate anion at the terminal double bond in-
meric form by eliminating water,[35] which was con- stead of nucleophic substitution at the alcohol has
firmed by NMR and mass spectroscopy. The formed been described.
HCl in the above process converts sulfinate salt 2 to
sulfinic acid nucleophile IV. Presumably, in the pres-
ence of a nucleophile, the ether is polarized by both Experimental Section
FeCl3 and/or HCl and generates an incipient benzylic
carbocation III. The stability of the intermediate, ben- Typical Experimental Procedure for the Direct
zylic carbocation is well-documented and has been Sulfonylation of Alcohols
the subject of theoretical and experimental studies.[29]
To a solution of alcohol (1 mmol), sodium arenesulfinates
The nucleophilic attack of the sulfinate anion onto
(1.5 mmol) and FeCl3 (15 mol%) in dichloromethane
the benzylic carbocation generates the desired sulfo-
nyl ether 3.
(3 mL), TMSCl (1.2 mmol) was added. The reaction mixture
was stirred at 458C and monitored by TLC. After comple-
tion of the reaction, the reaction mixture was quenched with
NaHCO3 solution. The aqueous layer was extracted with
ethyl acetate (3ꢂ20 mL), and the combined organic phases
were dried over anhydrous Na2SO4, concentrated under
vacuum and purified by column chromatography on silica
gel to afford the pure product. All products were character-
ized by IR, 1H NMR, 13C NMR and mass spectroscopic tech-
niques.
On the other hand, in the case of homoallylic alco-
hols, a plausible reaction course is proposed as shown
in Scheme 3. The silylation of homoallylic alcohol 4
with TMSCl takes place as the first step and gives the
intermediate trimethylsilyl ether V and hydrochloric
acid. The coordination of iron to the double bond of
the homoallyl alcohol transfers it from a terminal po-
sition to an internal position through migration of hy-
dride[36] from the C-2 position to the C-4 of the chain
VI. Then, the structure of p-allyl-iron VII[37] is built-
up through the departure of the trimethylsilyl-protect-
ed hydroxy group. Attack of the p-allyl-iron complex
with sulfinate anion IV, which was generated from the
reaction of sulfinate salt and HCl, gives the final
product allylic sulfones 5.
Acknowledgements
MAR and PSR thank the Council of Scientific and Industrial
Research (CSIR), India, for Senior Research Fellowships.
In summary, we have developed a new and efficient
FeCl3-catalyzed direct sulfonylation of benzylic, allylic
and homoallylic alcohols with high atom economy
using TMSCl as an additive. The new catalytic reac-
tions presented in this paper could be a meaningful
addition to the existing methods with preformed or
activated electrophiles and the use of stoichiometric
amounts of base and/or metal salts. Additionally, a
first example of the FeCl3-catalyzed direct sulfonyla-
tion of homoallyl alcohols through nucleophilic addi-
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