Catalytic, metal-free sulfonylcyanation of alkenes: Via visible light organophotoredox catalysis

Article abstract of DOI:10.1039/c8cc00547h

The group transfer radical addition of olefins with tosyl cyanide has been accomplished via visible light-induced organophotoredox catalysis. A diverse array of olefins is amenable to this protocol, furnishing β-sulfonyl nitriles with excellent efficiency under metal-free and redox-neutral conditions. A closed catalytic cycle is operative in this transformation, providing complementary reactivity to the classic radical chain process.

Full text of DOI:10.1039/c8cc00547h

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Catalytic, Metal-free Sulfonylcyanation of Alkenes via Visible light
Organophotoredox Catalysis
Jianfeng Sun,†,a Peng Li,†,a Lei Guob, Fang Yu,a Yu-Peng He,*,a and Lingling Chu*,b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
The group transfer radical addition of olefins with tosyl cyanide
has been accomplished via visible light-induced organophotoredox
catalysis. A diverse array of olefins is amenable to this protocol,
furnishing β-sulfonyl nitriles with excellent efficiency under metal-
free and redox-neutral conditions. A closed catalytic cycle is
operative in this transformation, providing complementary
reactivity to the classic radical chain process.
Alkenes are abundant and privileged building blocks in chemical
and material industries, and recently difunctionalization of alkenes
has been redeemed as
a powerful strategy for building up
molecular complexity from simple starting materials in an
economical and straightforward fashion.1 Besides the organometall-
ic additions,1a-c radical–based additions to alkenes also represent a
versatile approach to functionalize alkenes with the simultaneous
and regioselective installation of two functionalities.2 One of the
most widely employed transformations of this type is the atom
transfer radical addition (ATRA) reactions of olefins with alkyl
halides, which enables the formation of C-C and C-X bonds in an
atom- and step-economic way.3 Recent effort has been devoted to
develop efficient ATRA reactions employing safer reagents and
environmental friendly and mild conditions. Seminal works by the
group of Stephenson4 and others5 have elegantly demonstrated the
application of visible light-induced photoredox catalysis6,
a
Figure 1. Organophotoredox catalyzed sulfonylcyanation of alkenes.
powerful strategy for the development of useful transformations, to
facilitate ATRA addition to alkenes with alkyl halides, advancing the
ATRA technology with solar energy in a simple and efficient way.
More recent advances have revealed that the ability of organic pho-
toredox catalysts to facilitate ATRA reactions7 as well as atom trans-
fer radical polymerizations8 under metal-free conditions. To the
best of our knowledge, however, visible light-mediated ATRA-type
group transfer radical addition of alkenes remained underexplored,
although this approach would enable the net addition of two funct-
ional groups beyond halogen atoms under mild conditions.9
The alkyl nitriles10 and sulfones11 are important motifs prevalent
in pharmaceuticals, agrochemicals, natural products, and materials.
Several drugs, such as anti-diabete drug vildagliplin, anti-breast
cancer drug anastrazole, calcium channel blocker verapamil, and
anti-prostate cancer drug bicalutamide, all contain the key nitrile or
sulfone moieties. Moreover, nitriles are versatile precursors for
aldehydes, carboxylic acids, amides, and other important
functionalities in organic synthesis.12 As such, the concomitant
incorporation of a cyano and sulfonyl group into one molecule, the
regioselective sulfonylcyanation of alkenes, would serve as an
attractive entry to the synthesis of alkyl nitriles and sulfones.
Herein, we describe the organo-photoredox catalyzed regioselec-
tive sulfonylcyanation of alkenes under mild, metal-free, and redox-
neutral conditions, providing facile access to a wide range of
α-sulfonyl nitriles with excellent atom and step economy.
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Table 1. Optimization of the reaction conditions a
influence on the reaction efficiency, with polar solvent DMSO
providing the best result. The employment of less polar solvents
had a deleterious effect, and significantly low yields were obtained
in these cases (entries 6-8). This reaction is sensitive to air,
indicating a radical process involved in this transformation (entry 9).
Furthermore, control experiments revealed that importance of both
photocatalyst and visible light to the desired transformation, as no
product formations were observed in the absence of photocatalyst
or light (entries 11 and 12). Heating the reaction mixture under
dark conditions couldn’t promote this transformation (entry 13).
As revealed in Table 2, a diverse array of unactivated and active-
ted alkenes can undergo the desired regioselective sulfonylcyan-
ation with excellent efficiency under the metal-free and redox-
neutral conditions. The mild reaction conditions are compatible
with a wide range of functional groups, such as ketones, esters,
amides, bromides, chlorides, and boronic esters, providing
a
versatile platform for further synthetic manipulations (products 4–
14, 63%–97% yields). Remarkably, both alkyl halides and alkyl
boronic esters were competent substrates, affording the desired
products in high to excellent yields, where the halogen and boronic
atoms remained intact under visible light irradiation (products 4, 9–
10, 63%–95% yields). The resulting products can be further
employed to cross-coupling reactions via transition metal catalysis,
highlighting complementary ability of this photoredox technique.
With respect to the terminal alkenes, 1,1-di-substituted alkenes in
both cyclic and acyclic forms could undergo the radical addition
smoothly with efficient formation of quaternary carbon
stereocenters, and substituents at the α-position of alkenes has
little effect on the reaction yields (products 11–12, 16, 63%–80%
yields). Besides terminal alkenes, less reactive internal alkenes,
including cyclopentenes and cyclohexenes, proved to be highly
efficient in this transformation, delivering the corresponding nitriles
in good efficiency and moderate stereoselectivity (products 13–15,
60%–85% yields). Furthermore, naturally occurring bicyclic alkenes,
such as (+)-β-pinene and (+)-α-pinene, were shown to be viable
substrates, furnishing the ring-opening products 16 and 17 in 63%
and 85% yields respectively, further indicating the radical nature of
this protocol. Gratifyingly, the sulfonylcyanation reaction of
allylbenzene in a 4 mmol scale furnished the desired product 1 in
aReaction conditions: allylbenzene (0.1 mmol), TsCN (0.3 mmol), DMSO [1.2 M],
Eosin Y (2 mol%), N2, 90W blue LED, 20h. bDetermined by gas chromatography with
an internal standard.
Tosyl cyanide has been widely used as a cyanating agent in
radical processes, nevertheless producing tosylate as chemical
waste.13 Utilizing TsCN as cyano trapping agent as well as sulfonyl
radical4a, 14 source would be advantageous to atom economy of
reactions. Indeed, the groups of Fang and Barton independently
described the radical addition of alkenes with TsCN in the presence
of UV-light irradiation or radical initiators, proceeded by a radical
chain propagation process.15 While the requirement of an excess of
alkene substrates limited the utility of these transformations in late-
stage functionalizations of complex molecules. With this in mind,
we sought to develop a catalytic sulfonylcyanation of alkenes via an
alternative approach – a non-chain mechanism that may provide
opportunities to tune the reaction processes through catalyst
evaluation, and to increase the synthetic practicality by employing
substrate as the limiting reagent. We reported the development,
application, and the mechanistic studies of this transformation in
this communication.
Evaluation of this photoredox sulfonylcyanation strategy was
examined with allylbenzene as the model substrate. As shown in
Table 1, irradiation with
a 90W blue LED of a solution of
allylbenzene and TsCN in the presence of 2 mol% Eosin Y in DMSO
at room temperature delivered the desired β-sulfonyl nitrile
product 1 in 90% yield (Table 1, entry 1). Other metal-based
photoredox catalysts, such as Ir[dF(CF3)ppy]2(dtbbpy)PF6,
Ir(ppy)2(dtbbpy)PF6, and Ru(phen)3Cl2 that have been commonly
employed in visible light induced ATRA reactions,4, 5b also promoted
this transformation with slightly diminished efficiency (entries 2-4).
However, the use of benzophenone resulted in a dramatic decrease
in efficiency (entry 5). Not surprisingly, solvents played a big
Figure 2. Mechanistic Studies. A) Quenching study. B) Light-dark
Experiments; C) Laser set-up; D) Calculations of quantum yield and quenching
fraction; E) Determination of byproduct.
2 | J. Name., 2012, 00, 1-3
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Scheme 1. Organophotoredox-catalyzed sulfonylcyanation of alkenes. All yields are isolated yields; Diastereoselectivity was determined by 1H NMR analysis after
isolation. a4 mmol scale; bFrom β-pinene; cFrom α-pinene; dFrom 1,3-cyclohexadiene.
1.05 g, 88% yield, further indicating the synthetic potential of this formation of product was only feasible during periods of irradiation
photoredox manifold.
while no products formed during periods of dark (Figure 2B).
Moreover, this protocol could be further applied to activated Furthermore, we conducted the quantum yield measurements for
alkene system, including cyclic and acyclic vinyl ethers, affording a this photochemical reaction of allylbenzene and TsCN using a
variety of α-oxo nitriles in good to excellent yields (products 20–23, commercial 532 nm laser (photon flux of 2.44*10-7 Einstein s-1)
60−92% yield). Notably, enamides such as Cbz-protected dihydro- (Figure 2C).16 The calculated quantum yield value of Φ = 0.273,
pyrrole can be regioselectively functionalized, furnishing the α- indicating the involvement of long radical chain progress is unlikely
amino nitriles in synthetic useful yield (product 24, 60% yield). The (Figure 2D). To further preclude the occurrence of quite short chain
resulting β-Amino nitrile is a key structural core found in a number process, we calculated the hypothetical chain length of this
of medicinal agents including anti-diabetic drug Vildagliplin. reaction, with an assumption that the product was formed via
Additionally, we found dienes and aryl alkenes could be employed radical chain progress. The hypothetic chain length of 0.283,
with equal efficiency, as exemplified by 1,3-cyclohexadiene and calculated using quantum yield and quenching fraction, is less than
indene, to furnish the corresponding allyl and benzyl nitriles unity, which is not suggestive of a radical chain process. Moreover,
(products 18–19, 25, 72−79% yield).
5% yield of byproduct 26, formed via elimination of carbon cation
To probe the mechanism of this photoredox transformation, a intermediate, can be isolated under the standard condition,
number of preliminary mechanistic studies were conducted. suggesting that a radical-polar crossover mechanism is operative
Stern−Volmer fluorescence quenching experiments clearly demon- (Figure 2E).
strated that the excited state of photocatalyst Eosin Y can be quen-
On the basis of these observation, a proposed radical-polar
ched by TsCN (Figure 2A). Next, the light-dark experiment was crossover mechanism is depicted in Scheme 1. Irradiation of Eosin
conducted using alternative intervals of light and dark, and the Y2- with visible light could form an excited singlet state of *Eosin Y2-,
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triplet state *3Eosin Y2- 27. The highly reducing excited state of 27
[E (EY*/EY+•) = −1.15 V vs SCE in MeCN]17 could facilitate the
½
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½
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sulfonylcyanation of alkenes with TsCN via visible light-
mediated organophotoredox catalysis. This metal-free and
redox-neutral protocol is applicable to a wide array of alkenes
containing many important functional groups, incorporating
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A closed catalytic cycle is operative in this
transformation, providing complementary reactivity to the
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‡ We are grateful to the “Thousand Plan” youth program, the National
Natural Science Foundation of China (21702029), and the Shanghai Sailing
Program (17YF1400100), the National Natural Science Foundation of China
(21402078), and Foundation of Department of Education of Liaoning Province
(LJQ2015060) for support of this research.
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Graphic Abstract
A catalytic, redox-neutral group transfer radical addition of olefins with tosyl cyanide via visible light-induced
organophotoredox catalysis has been described.