Divergent Regio- and Stereoselective Gold-catalyzed Synthesis of α-Fluorosulfones and β-Fluorovinylsulfones from Alkynylsulfones

Article abstract of DOI:10.1002/chem.201703179

We developed a widely applicable, highly efficient synthesis of α-fluorosulfone and β-fluorovinylsulfone catalyzed by gold. Starting with alkynyl sulfone 1, an [Au]/HF/N-oxide system gives α-fluorosulfone 3 via a gold carbene intermediate, and, if no N-oxide is used, direct addition of HF to 1 gives vinyl sulfone 4 via a vinylfluoro gold intermediate. Both methods have good functional group tolerance and the reactions can be conducted in ambient atmosphere.

Full text of DOI:10.1002/chem.201703179

A Journal of
Accepted Article
Title: Divergent Regio- and Stereoselective Gold-catalyzed
Synthesis of α-Fluorosulfones and β-Fluorovinylsulfones from
Alkynylsulfones
Authors: Gerald Hammond, bo xu, xiaojun zeng, and shiwen liu
This manuscript has been accepted after peer review and appears as an
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To be cited as: Chem. Eur. J. 10.1002/chem.201703179
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Divergent Regio- and Stereoselective Gold-catalyzed Synthesis of
-Fluorosulfones and -Fluorovinylsulfones from Alkynylsulfones
Xiaojun Zeng,[a] Shiwen Liu, [a] Gerald B. Hammond[b], * and Bo Xu[a], *
Abstract: We developed
a
widely applicable, highly efficient
of activator and director in the nucleophilic fluorination of an
alkyne. Using this approach, alkynyl sulfone 1, [Au]/HF/N-oxide
yields-fluoro-sulfone 3 via a gold carbene intermediate in the
presence of N-oxide, and furnishes vinyl sulfone 4 by direct
addition of HF via a fluoro vinyl gold intermediate when the N-
oxide is absent (1c).
synthesis of -fluorosulfone and -fluorovinylsulfone catalyzed by
gold. Starting with alkynyl sulfone 1, an [Au]/HF/N-oxide system
gives -fluorosulfone 3 via a gold carbene intermediate, and, if no N-
oxide is used, direct addition of HF to 1 gives vinyl sulfone 4 via a
vinylfluoro gold intermediate. Both methods have good functional
group tolerance and the reactions can be conducted in ambient
atmosphere.
Sulfones are important biological targets[1] and versatile
synthetic building blocks.[2] In this regard, the sulfonyl group is
one of the strongest electron withdrawing groups, and, as such,
it can greatly increase the acidity of an -proton. Certainly, a
sulfone with an -proton has been widely used as a nucleophile
in several C-C bond forming reactions, such as the Julia
olefination[3] and the Ramberg-Bꢀcklund reaction (Scheme 1a).[4]
Vinyl sulfones, on the other hand, are among the most electron
deficient/reactive alkenes and have been widely used as
[2b, 5]
partners in ionic, radical additions and cycloadditions,
or in
the total synthesis of natural products (Scheme 1a).[6] Their
importance is underlined by a recent literature review that stated
that over 42 new syntheses of vinyl sulfones have been reported
in the last 5 years alone.[5a] Given fluorine’s preeminence in
medicinal chemistry[7] and the sulfonyl group’s importance as an
organic building block, their juxtaposition on a vinyl or carbonyl
template (fluoro-A or fluoro-B in Scheme 1) should lead to
desirable motifs in medicinal or synthetic chemistry but their
syntheses are quite challenging. For examples, Hu[8] and
Prakash[9] have demonstrated the fluoro-A type compounds
were versatile fluorinated building blocks. In fact, the synthesis
of fluoro-A type compounds has only been reported via the
electrophilic fluorination of precursor C, using expensive, low-
atom economic reagents and harsh conditions that often give
rise to difluorination byproducts.[8] The other reported
alternatives are to utilize sophisticated fluorinated synthons.[10]
Fluorinated vinyl sulfones (fluoro-B) are even harder to prepare;
indeed, only perfluorinated vinyl sulfones are hitherto known
(Scheme 1b).[11]
Scheme 1. Background and overview of approach.
In our previous work, we found that HF was highly
compatible with cationic gold catalysts, this was demonstrated
by the synthesis of -fluoroketone via HF insertion to a gold
carbene intermediate[12] or by the synthesis of fluoroalkenes
through the addition of HF to a cationic gold activated alkyne.[13]
These methods proved efficient for terminal alkynes; internal
alkynes showed low or no reactivity, and the regioselectivity
depended on steric and electronic biases at either end of the
alkyne. Also, there are many progresses in gold catalyzed
fluorination of alkynes using electrophilic fluorination reagents.[14]
For our HF insertion and addition protocols, we used the
fluorination of alkynyl sulfone 1a as our model reaction (Table 1).
The method we used to generate a gold carbene[15] was the gold
catalyzed alkyne oxidation by N-oxide.[16] N-oxide is a mild
oxidant, so we expected good functional group tolerance. Initially,
we chose dichloropyridine N-oxide 2a as our oxidant and
pyridine-HF as our fluorine source. Screening of various silver
activators indicated that AgNTf2 was slightly better than AgOTf
and AgSbF6 (Table 1, entries 1-3). We proceeded to investigate
the effect of the ligand (Table 1, entries 4-7).[17] Buchwald type
ligands gave slightly better results, and, among them, JohnPhos
gave the best chemical yield (Table 1, entry 6). Recently, we
had demonstrated that excess amounts of silver almost always
Herein, we report a widely applicable, highly efficient and
divergent synthesis of fluoro-A and fluoro-B, catalyzed by gold
(Scheme 1c). The common precursor, alkynylsulfone 1, is
readily accessible, and the fluorinating reagent, hydrogen
fluoride (HF), is one of the most atom economical fluorine
sources.[7b] Our strategy hinges on the sulfonyl group’s dual role
[
]
a
X. Zeng, S. Liu and Prof. B. Xu
College of Chemistry, Chemical Engineering and Biotechnology
Donghua University, Shanghai 201620 China
Email: bo.xu@dhu.edu.cn
[b]
Prof. G. B. Hammond
Department of Chemistry, University of Louisville
Louisville, KY 40292 USA.
E-mail: gb.hammond@louisville.edu
Supporting information for this article is given via a link at the end of
the document. ((Please delete this text if not appropriate))
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had a deleterious effect on the reactivity of gold catalysts,[18] and
that a preformed gold catalyst (e.g., L-Au-NTf2)[19] rendered
better results. Indeed, a preformed JohnPhos-Au-NTf2 catalyst
gave a good result in our reaction (Table 1, entry 8). Among
other N-oxides tested, 8-methylquinoline N-oxide 2b gave
poorer yields (Table 1, entry 9) and pyridine N-oxide 2c could
not mediate this reaction at all (Table 1, entry 10). We found that
fluoro vinyl sulfone 4a could be obtained by simply removing N-
(Table 2 , 3g), small rings, such as cyclopropyl (Table 2 , 3h),
the alkenyl group (Table 2 , 3i), simple or functionalized alkyl
groups (Table 2 , 3j-3m). We also evaluated more [R1, R2]
combinations, such as [R1 = aryl, R2 = aryl] (Table 2, 3n-3u), [R1
= aryl, R2 = alkyl] (Table 2, 3v-3x), [R1 = alkyl, R2 = aryl] (Table 2,
3y), [R1 = alkyl, R2 = heteroaromatic] (Table 2, 3z), [R1 = alkenyl,
R2 = aryl] (Table 2, 3aa) and [R1 = alkyl, R2 = alkyl] (Table 2,
3ab). All of these combinations gave good yields of product 3.
Only when R1 or R2 were alkenyl groups, the yields were
moderate (Table 2, 3i and 3aa). This last result could be
rationalized by considering the relative instability of the starting
material and/or product under the reaction conditions. It should
be noted that functional groups as diverse as ketones (Table 2,
3p), esters (Table 2, 3q, 3u, 3v), ethers (Table 2, 3d, 3r), nitriles
(Table 2, 3t), benzylic (Table 2, 3m), sulfonates (Table 2, 3w,
3x), or alkenes (Table 2, 3i, 3aa) did not hinder the efficiency of
our method.
oxide
2
(Table 1, entry 11). Other solvents (DCM,
fluorobenzene) led to poorer yields (Table 1, entries 12-13). No
reaction took place in the absence of gold catalyst (Table 1,
entry 14).
Table 1.Screening of reaction conditions.[a]
Table 2. Scope for the synthesis of-fluoroketone 3.a
Yield(%)[b]
Entry
N-Oxide Solvent Product
[Au]+Activator
1
2
PPh3AuCl+AgOTf
PPh3AuCl+AgNTf2
PPh3AuCl+AgSbF6
(RO)3PAuClc+AgNTf2
Dppf(AuCl)2+AgNTf2
JohnPhosAuCl+AgNTf2
SPhosAuCl+AgNTf2
JohnPhosAuNTf2
JohnPhosAuNTf2
JohnPhosAuNTf2
JohnPhosAuNTf2
JohnPhosAuNTf2
JohnPhosAuNTf2
-
2a
2a
2a
2a
2a
2a
2a
2a
2b
2c
-
PhCF3
PhCF3
PhCF3
PhCF3
PhCF3
PhCF3
PhCF3
PhCF3
PhCF3
PhCF3
PhCF3
DCM
3a
3a
3a
3a
3a
3a
3a
3a
3a
3a
4a
4a
4a
-
58
60
3
55
4
62
5
57
6
85
7
50
8
89 (82d)
40
9
10
11
12
13
14
NR
74 (64d)
68
-
-
Ph-F
63
2a
PhCF3
0
Reaction conditions: 1a (0.2 mmol), N-Oxide 2 (0.3 mmol), pyridine-HF (1.3
mmol HF, 6.5 equiv), L-AuCl (2.5 mol%), activator (2.5 mol%), solvent (0.4
[b]
mL), RT in a sealed polypropylene tube for 8 h.
analysis. [c] R = 2,4-di-tBu-C6H3-. [d] isolated yield.
Determined by GC-MS
a Reaction conditions: alkyne 1 (0.2 mmol), N-Oxide 2a (0.28 mmol), pyridine-
HF (0.8 mmol HF), JohnPhosAuNTf2 (2.5 mol %), PhCF3 (0.5 mL), rt. All yields
are isolated yields.
With optimized conditions in hand, we explored the scope
and functional group tolerance of our HF insertion protocol
(Table 2). First, we evaluated the effect of R1 substitution on the
alkynylsulfone 1 (Table 2, 3a-3f). The substitution pattern (meta,
para) of R1 played a small role; good yields were obtained
regardless (Table 2, 3a-3f). Then we evaluated the effect of R2
substitution (Table 2, 3g-3m). The reaction tolerated a wide
variety of R2 substituents: heteroaromatics, such as thiophene
The results illustrated in equations 1-3 underscore the
importance of the sulfonyl group: 1ad furnished the diketone
product 6a whereas alkynylketone 1ae and phosphonyl alkyne
1ag showed no reactivity under the same reaction conditions.
The formation of 6a was attributed to the fact that the
corresponding gold carbene intermediate is electron rich, which
makes it easily oxidized by N-oxide.[16h]
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The substrate scope of our HF addition protocol is
depicted in Table 3. First, we evaluated the effect of R1
substitution of alkynylsulfone 1 on the reaction (Table 3, 4a-4d):
electron rich and electron deficient substituents only had a very
small effect on the chemical yields. We then evaluated the effect
of R2 substitution of 1 (Table 3, 4e-4i). Similarly, the effect of
both electron rich and electron deficient substituents was minor.
We also evaluated other [R1, R2] combinations, such as [R1 =
aryl, R2 = alkyl] (Table 3, 4j-4l, 4n, 4o, 4s, 4t), [R1 = alkyl, R2 =
aryl] (Table 3, 4q, 4r), [R1 = aryl, R2 = alkenyl] (Table 3, 4p), [R1
= alkenyl, R2 = aryl] (Table 3, 4u). All of these combinations
gave good yields of product 4, demonstrating that the substrate
scope was broad. It should be noted that acid sensitive groups
such as cyclopropyl and alkenyl were well tolerated (Table 3, 4l).
reagent such as DMPU-HF.[13e] It is surprising to find that this HF
addition pathway is completely inhibited by the addition of N-
oxide 2 because only the carbene insertion product 3 was
obtained. As both reactions proceeded at room temperature, we
proposed that the strong hydrogen bonding interaction between
HF and N-oxide 2 precluded the HF addition pathway. Actually,
HF is one of the strongest hydrogen bonding donors and N-
oxides are among the strongest hydrogen bonding acceptors.[20]
Their hydrogen bonding interaction reduces significantly the
nucleophilicity of HF, which, in turn, leads to the shutdown of the
HF addition pathway (Scheme 2, bottom). Because N-oxide is a
much stronger nucleophile, the addition of N-oxide to the alkyne
is not inhibited, which leads to the formation of reactive gold
carbene intermediate Au-3.[21] The hydrogen bonding interaction
between HF and Au-2 may accelerate the formation of gold
carbene Au-3. This behavior could explain the very mild
conditions needed for the formation of 4.
Table 3. Scope for the synthesis of fluoro-vinyl Sulfones4.a
Scheme 2. Proposed mechanism for the formation of 3 and 4.
The advantages of the alkynylsulfone starting material and
the versatility of fluorosulfone 3 are clearly underscored in
Scheme 3.
a Reaction conditions: alkyne 1 (0.2 mmol), pyridine-HF (HF content 0.8 mmol),
JohnPhosAuNTf2 (2.5 mol %), PhCF3 (0.5 mL), RT. All yields are isolated
yields.
Scheme 2 illustrates the proposed mechanism. In the
absence of N-oxide 2, the addition of HF to the gold activated
alkyne
1 generates a vinyl gold intermediate Au-1, its
subsequent protodeauration leads to the addition product 4. In
our opinion, the presence of a strongly activating group such as
sulfonyl, renders unnecessary
a more reactive HF-based
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Keywords: -fluorosulfone, gold carbene, fluorination, hydrogen
fluoride, N-oxide
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fluorovinylsulfones from a common alkynyl sulfone precursor.
Our fluorine source is the most economical fluorine source
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fluorination systems based on HF/gold system are currently
being investigated in our laboratories.
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Acknowledgements
We are grateful to the National Science Foundation of China
(NSFC-21472018) and China Recruitment Program of Global
Experts for financial support. G.B.H. is grateful to the National
Science Foundation (CHE-1401700). XZ is grateful to China
Scholarship Council for financial support.
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We developed a widely
applicable, highly efficient
synthesis of -
Xiaojun Zeng, Shiwen Liu,
Gerald B. Hammond* and
Bo Xu*
fluorosulfones and -
fluorovinylsulfones from a
common alkynyl sulfone
precursor. The reactions
exhibited high functional
groups tolerance and
needed only ambient
atmosphere..
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