Visible-Light-Induced Palladium-Catalyzed Carbocyclization of Unactivated Alkyl Bromides with Alkenes Involving C-I or C-B Coupling

Article abstract of DOI:10.1021/acs.joc.0c00077

A palladium-catalyzed, photochemical tandem cyclization/dicarbofunctionalization of unactivated alkyl halides containing an alkene moiety offers an appealing route to produce five- or six-membered rings in a redox-neutral fashion. Multisubstituted carbo- and heterocyclic compounds were prepared through the formation of new C-B or C-O bonds, which provides a convenient synthetic route for further transformations. This protocol is characterized by the reaction of alkene regio- and stereoselectivities, good functional group compatibility, wide substrate scope, and mild reaction conditions.

Full text of DOI:10.1021/acs.joc.0c00077

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Note
Visible Light-Induced Palladium-Catalyzed Carbocyclization of
Unactivated Alkyl Bromides with Alkenes Involving C-I or C-B Coupling
Jun-wei Ma, Xi Chen, Zhao-Zhao Zhou, and Yong-Min Liang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.0c00077 • Publication Date (Web): 02 Jul 2020
Downloaded from pubs.acs.org on July 2, 2020
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Visible Light-Induced Palladium-Catalyzed Carbocyclization of Unactivated
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Alkyl Bromides with Alkenes Involving C−I or C−B Coupling
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Jun-wei Ma, Xi Chen, Zhao-Zhao Zhou and Yong-Min Liang*
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State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P.R. China
Abstract
A palladium-catalyzed, photochemical tandem cyclization/dicarbofunctionalization of
unactivated alkyl halides containing an alkene moiety offers an appealing route to produce
five- or six-membered rings in a redox-neutral fashion. Multisubstituted carbo- and
heterocyclic compounds were prepared through the formation of new C–B or C–O bonds,
which provides a convenient synthetic route for further transformations. This protocol is
characterized by the reaction of alkene regio- and stereoselectivities, good functional group
compatibility, wide substrate scope, and mild reaction conditions.
Increased attention is being paid to the development of pharmacophore-, biological
molecule- and organic material-relevant heterocycles (e.g., pyrrolidines, tetrahydrofurans,
and piperidine) or carbocycles.1 Over the last few years, continuous research has successfully
extended the scope of manifold cyclic products with numerous elegant versions. The
functionalized cyclic motifs (iodine-functionalized or boron-functionalized compounds),
premanufactured alkyl electrophiles, can serve as versatile building blocks for further
structural elaboration by the derivatization of their self-contained carbon-iodine or
carbon-boron bonds.2 The ability to increase cyclic framework complexity captured our
interest in this type of synthesis.
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The 1,2-dicarbofunctionalization/cyclization of substituted alkenes with organic
electrophiles and organometallic reagents is an appealing method for the stereoselective
synthesis of valuable (hetero)cyclic compounds amenable to a single operational fashion.3
Typically, previous studies have focused on aryl/vinyl halides, unactivated alkyl iodine, and
activated alkyl halides (bearing a C(sp3)−X affected by the in situ activation of an
electron-withdrawing group, π-system, or heteroatom) for application in intramolecular cross
coupling with alkenes (Scheme 1).4 The extension to widely unactivated alkyl bromides
remains a long-standing challenge owing to the inherent energetic barrier of high redox
potentials for the activation.5 Fortunately, there are still numbers of strategies6 available to
achieve the abovementioned objective, in which the unactivated alkyl halides commonly act
as electrophilic alkyl sources7 participate in 1,2-dicarbofunctionalization of diverse
substituted alkenes. A successful example is that a breakthrough has been realized by the Ito
group for the copper(I)-catalyzed borylative radical cyclization of unactivated alkyl halides
with bis(pinacolato)diboron6a, which facile access to organoboron compounds with high
stereoselectivity. However, the visible-light-mediated photoredox processes of unactivated
carbon–halogen bonds via single-electron transfer (SET) scission are less explored, which
presents us with practical demands.2e, 8
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Visible light photocatalysis, an efficient and waste-minimizing process, is a powerful
approach that is used in modern radical chemistry;9 this method allows the rapid generation
of carbon-centered radicals to access new reactivity.4c, 4e, 10 The abovementioned advantages
exist because the relatively narrow redox potential window and limited photosensitizers of
typical photocatalysis hinder the potential applications of unactivated alkyl bromides. These
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questions provide a considerable motivation to study the potential of photoinduced
palladium catalysis in reaction development. Based on a previous study, which demonstrated
the palladium-catalyzed hydrodehalogenation and Br/D exchange of inactivated aryl and
alkyl halides in photocatalytic reaction (Scheme 1),11 we questioned whether palladium
catalyst-mediated radical initiation/tandem cyclization could be used to enable the
construction of functionalized (hetero)cyclic organic compounds under visible light
irradiation.
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We discovered that the optimized conditions were suitable for photoinduced palladium
and allowed to avoid potential pitfalls including: i) fast protodehalogenation or premature
β-hydride elimination before radical oxidative addition to substituted olefins,12, 13 and ii)
unwanted sp2-hybridized or sp3-hydrogenated processes of a cyclized intermediate rather
than trapped by an iodine/boron source.14 However, currently, there are no practical
intramolecular cyclization versions available to access valuable cyclic motifs involving the
concomitant introduction of carbon−iodine, and previous borylative radical cyclization
methods for the transition metal-catalyzed borylation products are restricted to the
formation of 5-membered rings.
Scheme 1: Strategies for the Carbofunctionalization of Alkyl Halides.
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This approach is an ideal entry to provide both five- and six-membered carbo- and
heterocyclic products containing a functionalized alkyl iodide (boride) moiety, which is
characterized by good to excellent diastereoselectivities and wide substrate scope of
polysubstituted cyclic compounds (Scheme 1). We initiated our investigation by probing
suitable conditions for the palladium-based systems that employed inexpensive potassium
iodide as an iodine atom donor or accessible bis(pinacolato)diboron as an applicable boron
reagent with challenging catalyzers, solvents, and bases (See ESI† for details).
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Scheme 2: Reaction Scope for the Synthesis of Iodine-substituted Ring Compounds.a, b
a Reaction conditions: 1 (0.2 mmol), 2 (0.6 mmol), [Pd] (3 mol %), Cs2CO3 (0.3 mmol), THF (1.0 mL), blue LED, rt,
b
24 h, and under argon atmosphere, yields of isolated products, X is equal to bromine unless otherwise noted.
Diastereoselectivity was determined by 1H NMR analysis, see the Supporting Information for details. This
c
reaction was performed in 12 h.
First, we screened the iodization of unactivated alkyl bromides under optimized conditions.
An assortment of primary and secondary alkyl bromide substrates containing internal or
terminal alkenes were prepared according to Scheme 2; these compounds were amenable to
an effective synthetic route with high regio- and stereoselectivities. Functionalized acyclic
starting primary and secondary bromides allow to access important monocyclic products
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3a-3j (e.g., pyrrolidines, tetrahydrofurans, and carbocycles) with a broad range of functional
groups (e.g., alkanes, aromatics, esters, ethers, esters, acetals, and sulfonamides). The steric
hindrance of 3d negatively affects the transformation with a moderate yield (54%). The 5-exo
carbocyclization of primary alkyl bromides was successful with disubstituted alkenes (entries
3c-3d) and terminal alkene. However, neither styrenes nor tetrasubstituted alkenes were
suitable for this strategy. Instead, 3o and 3p were rapidly converted to
alkyl-Mizoroki-Heck-type products15 in excellent yields. The efficient construction of bicyclic
frameworks 3k-3n can be built in reasonable yields using this protocol. Alkyl bromides
bearing β-substituents 3h-3n provided the corresponding products with good to reduced
reactivity, albeit with a favourable stereoselectivity. We attribute the reduced yields to the
relative feasibility of both possible reductive eliminations and hydrodehalogenation of the
initially generated alkyl radical.
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By comparing reactions with similar structures, it is determined that in general, the
primary bromides 3a reacted more efficiently than the secondary bromides 3e. This
approach was successfully extended to unactivated alkyl iodine 3a, and the iodization
reaction occurred in the absence of additional potassium iodide without significantly
affecting the reaction efficiency. As demonstrated by the 6-exo cyclization of N-heterocycles
3b, this radical cyclization reaction is not limited to the five-membered ring synthesis.
Scheme 3: Reaction Scope for the Synthesis of Boron-substituted Ring Compounds.a, b
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a Reaction conditions: 1 (0.2 mmol), 3 (0.4 mmol), [Pd] (5 mol %), ligand (10 mol %), K2CO3 (0.3 mmol), DMSO (1.0
mL), blue LED, rt, 24 h, and under argon atmosphere, yields of isolated products, X is equal to bromine unless
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otherwise noted. b Diastereoselectivity was determined by H NMR analysis, see the Supporting Information for
details. c This reaction was performed in 12 h. d A solution of pinacol (0.80 mmol) in triethylamine (0.70 mL) was
added to the mixture, 2 h, rt. e Pd(PPh3)4 was employed instead of Pd(PhCN)2Cl2, without additional ligands.
After assessing the scope of practicable route that afforded desired alkyl iodides, we
continued to examine the use of the borylation system in intermolecular cross-coupling
(Scheme 3). Both the six-membered alkylboration synthesis (5b) and the iodoalkyl group of
tosylamide substrate cyclization (5a) underwent effective coupling under optimized
conditions. In addition, the visible light-mediated alkylboration reaction tolerated
modification on the primary and secondary bromoalkyl groups, as demonstrated by the
formation of pyrrolidines (5a, 5c), tetrahydrofurans (5e, 5f), carbocycles (5h), and
spiro-heterocycles (5d, 5g) with similar or increased yields. The high diastereoselectivity of
5d (and 3m) is a response to the stabilization of the chair conformation by the anomeric
effect. The byproduct 5l was observed in the trisubstituted alkene example, which was
attributed to the high propensity toward elimination to the terminal alkene product, and no
reaction occurred in the absence of bis(pinacolato)diboron.
Meanwhile, we investigated the reactivity of other diboron reagents.
Bis(catecholato)diborane (B2cat2) proved to be a competent boron source, and the reaction
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proceeded smoothly to form an unstable the catecholboryl derivative. The boronic ester
could be transformed into the corresponding alcohol 5j after oxidative work up.16
Furthermore, 5a also could be obtained after transesterification with pinacol in a 53% yield.17
Bis(neopentylglycolato)diboron (B2neo2) also reacted as anticipated to give boryl-containing
N-heterocycle derivative 5i in a moderate yield.
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Two examples were conducted on a larger scale to demonstrate the practical utility of the
above methods (Scheme 4). As representative examples, the iodization and the borylation of
1a on a 3.15 mmol scale offered feasible gram scale synthesis of 2a in 43% yield and 5a in
37% yield, respectively.
Scheme 4: Scale-up Experiment.
To obtain mechanistic insight into the current iodization and borylation reactions,
mechanistic studies were carried out with radical trapping experiments and radical clock
reactions (Scheme 5), which indicated that these photoinitiated reactions likely proceeded
via a free-radical pathway and a 5-exo-trig radical intermediate was present in each catalytic
cycle. The iodization or borylation experiments did not afford any detectable amount of
product 3a or 5a when the reactions of 1a were carried out in the presence of TEMPO (1.3
equiv.). The addition of 1,1-diphenylethylene (1.5 equiv.) to standard reaction mixture also
displayed apparent inhibition effects by forming the adduct 6 with yields of 67% and 52%,
respectively. Next, two radical clock experiments were performed by using the cyclopropyl
moiety adjacent to olefin 7 as a radical scavenger. The ring-closure product 8 was obtained
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via radical rearrangements and the isolated yields in the respective catalysis were measured
to be 27% and 35%, respectively. The cyclopropyl-bearing substrate (E)-9 allow to access the
corresponding ring-opened products 10 and 11 upon visible-light irradiation, providing
additional supports to the radical nature of the transformation.
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Scheme 5: Radical Process Experiments.
To further investigate the influence of light irradiation on reaction progresses and the
photochemical behaviors of Pd species in these reactions, relevant experiments were
performed including light on-off experiments, UV/Vis absorption spectra studies and
Stern-Volmer luminescence quenching studies (See ESI† for details). The standard iodization
and borylation reactions were intermittently exposed to blue-light while monitoring
conversion (Scheme 6). It was found that the conversions ceased upon removal from
irradiation and continued upon additional irradiation. We speculated that these systems may
be amenable to photoinduced palladium catalyses which required constant irradiation,
rather than just photoinitiated radical-chain processes.
Scheme 6: Influence of Light Irradiation.
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Scheme 7: UV/Vis Absorption Spectra Studies.
Next, we measured UV/Vis absorption spectra of the Pd catalysts in the absence and the
presence of reaction components (Scheme 7 and Figure S1-S4). Broad absorbances were
observed in the region 400-500 nm under the iodization and borylation reactions. Notably,
two new peaks (λmax = 315 nm and 365 nm) were observed when Pd(PPh3)4 and 1a, as well
as the reaction mixture, were stirred under blue-light irradiation for 5min (Scheme 7c). This
phenomenon is similar with results demonstrated by others.9c In addition, A new peaks
(λmax = 295 nm) was observed, indicative of the possibility that K2CO3 may participate in the
construction of a photoabsorbing Pd(0) species in the borylation system (Scheme 7d).
Furthermore, fluorescence quenching experiments and Stern–Volmer studies (Scheme 8)
demonstrated that the alkyl bromides quenched the excited Pd species in line with the
envisaged SET event to afford the alkyl radical.
Scheme 8: Stern-Volmer Luminescence Quenching Studies.
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Scheme 9: Plausible Mechanism.
Based on the prior works and our observations, a plausible reaction mechanism is
proposed in Scheme 9. Our design is based on the hypothesis that rather than as a simple
initiator, palladium acts as a true catalyst in both catalytic cycles. The palladium complex,
which is generated by the reduction of bis(benzonitrile)palladium(II) chloride with
triphenylphosphine under the borylation conditions, exhibits blue light absorption and
provides a photoexcited Pd(0)L species A. A transfers an electron to an oxidative quencher
and produces a putative palladium(I) intermediate B and a carbon-centered radical C. Alkyl
radical C attacks one unsaturated bond to deliver a 5-exo cyclization intermediate D. In the
borylation catalyst cycle, the subsequent recombination with Pd(I)Br generates the key Pd(II)
species
E
via the SET process. Base-promoted transmetalation18 of
E
with
bis(pinacolato)diboron provides a new intermediate, which leads to the observed final
product during the regeneration of the Pd(0) catalyst. In addition, during the iodization stage,
the coordination of KI to the palladium (I) center of B offers another palladium species F. This
is followed by the iodization of D to generate the desired heterocyclic iodide formed by the
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iodine atom transfer from the F catalyst. Simultaneously, oxidized palladium returns to its
original oxidation state that can participate in the new Pd-catalyst turnover.
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In summary, a palladium-catalyzed intramolecular version provides a straightforward route
to access iodine- or boron-substituted cyclic frameworks (e.g., pyrrolidine, piperidine,
cyclopentane, and tetrahydrofuran) by photocatalysis that are difficult to prepare by
conventional methods. The optimized conditions form the kinetically favorable cyclization of
electrophilic addition to alkene. Alkyl bromides and alkyl iodines can be developed, and a
series of tests on boron reagents is devoted to extend the synthetic application. In addition,
several reductive cyclization byproducts can be observed with photoinduced palladium
catalysis, and some of them are absent from the literature. Further studies along the tandem
cyclization/functionalization line are currently in progress.
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Experimental Section
General Methods. For Column chromatography, 200-300 mesh silica gel was employed.
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Analytical TLC was performed with silica gel GF254 plates. 1H NMR (400 MHz) and C NMR (100
MHz) were recorded in CDCl3 using TMS as internal standard. All products were further
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characterized by high resolution mass spectra (HRMS); copies of their H NMR and 13C NMR
spectra are provided. The HRMS was obtained using a Q-TOF instrument equipped with ESI
source. Commercially available reagents were used without further purification. All solvents were
dried under standard method. Photochemical reactions were conducted in a reaction box (Kessil
brand Blue LED Grow Light, 440 (± 15) nm, 75W, 5-7 cm away, with cooling fan to keep reaction
temperature between 20 °C and 30 °C, and the irradiation vessels are Schlenk tubes of
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borosilicate glass). Starting materials were prepared in analogy to several literature procedures;
spectral data were in agreement with literature values.3g, 6b, 6e, 19
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General Procedures for the Synthesis of the Products 3.
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To a Schlenk tube were added unactivated alkyl bromides 1 (0.2 mmol, 1.0 equiv), potassium
iodide 2 (0.6 mmol, 3.0 equiv), palladium catalyst (0.006 mmol, 3 mol %), and Cs2CO3 (0.3 mmol,
1.5 equiv). The reaction vessel was evacuated and backfilled with Argon for three times, and then
injected 1.0 mL THF (0.2 M) into the tube. The reaction mixture was stirred under blue LED
irradiation at room temperature for 24 hours. After full conversion, the reaction mixture was
transferred into a separating funnel and 20.0 mL of distilled water and 5.0 mL of brine were
added. The resulting mixture was extracted with Et2O (20.0 mL *2) and combined organic layer
were dried over MgSO4, filtered and concentrated in vacuum. The product was purified by flash
column chromatography on silica gel with n-pentane/ethyl acetate as eluent to give the
corresponding product 3.
General Procedures for the Synthesis of the Products 5.
To a Schlenk tube were added unactivated alkyl bromides 1 (0.2 mmol, 1.0 equiv), boron
reagent 4 (0.4 mmol, 2.0 equiv), Bis(benzonitrile)palladium(II) chloride (0.01 mmol, 5 mol %),
PPh3 (0.02 mmol, 10 mol %) and K2CO3 (0.3 mmol, 1.5 equiv). The reaction vessel was evacuated
and backfilled with Argon for three times, and then injected 1.0 mL DMSO (0.2 M) into the tube.
The reaction mixture was stirred under blue LED irradiation at room temperature for 24 hours.
Then the reaction mixture was quenched with water (25 mL) and extracted with Et2O (20 mL × 3).
The combined organic layers were washed twice with water (15 mL each time) and brine (15 mL),
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dried over MgSO4. After filtration, the solvents were evaporated under reduced pressure. The
organic extracts was purified by flash column chromatography on silica gel with n-pentane/ethyl
acetate as eluent (to facilitate separation, a small amount of acetic acid is added in the solvent)
to give the corresponding product 5.
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Preparation of (1-tosylpyrrolidin-3-yl)methanol (5j).16
To a schlenk tube were added 1a (63.4 mg, 0.2 mmol, 1.0 equiv), bis(catecholato)diborane
(96.0 mg, 0.4 mmol, 2.0 equiv), Bis(benzonitrile)palladium(II) chloride (3.8 mg, 0.01 mmol, 5
mol %), PPh3 (5.3 mg, 0.02 mmol, 10 mol %) and K2CO3 (41.4 mg, 0.3 mmol, 1.5 equiv). The
reaction vessel was evacuated and backfilled with Argon for three times, and then injected 1.0
mL DMSO into the tube. The reaction mixture was stirred under blue LED irradiation at room
temperature. The reaction progress was monitored by GC analysis. Then the reaction mixture
was quenched with water (25 mL) and extracted with Et2O (20 mL × 3). The combined organic
layers were washed twice with water (15 mL each time) and brine (15 mL), dried over MgSO4.
After filtration, the solvents were evaporated under reduced pressure. Then 3.0 mL of MeOH,
NaOH (aq, 3.0 mL, 3M) and H2O2 (2.0 mL, 33%) were added to the organic extract and it was
cooled at 0 °C. After the schlenk tube was stirred at 0 °C to room temperature overnight,
saturated solution of Na2S2O3 was added to the mixture. The resulting mixture was extracted
with dichloromethane (7.0 mL *2) and combined organic layer were dried over MgSO4, filtered
and concentrated in vacuum. The product was purified by flash column chromatography on silica
gel to to afford the final product 5j.
Scale-up Experiment
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To a round-bottom flask were added unactivated alkyl bromides 1a (1.0 g, 3.15 mmol, 1.0
equiv), potassium iodide 2 (9.45 mmol, 3.0 equiv), palladium catalyst (0.095 mmol, 3 mol %), and
Cs2CO3 (4.73 mmol, 1.5 equiv). The reaction vessel was evacuated and backfilled with Argon for
three times, and then injected 15.7 mL THF (0.2 M) into the tube. The reaction mixture was
stirred under blue LED irradiation at room temperature for 24 hours. After full conversion, the
reaction mixture was transferred into a separating funnel and 30.0 mL of distilled water and 30.0
mL of brine were added. The resulting mixture was extracted with Et2O (50.0 mL *2) and
combined organic layer were dried over MgSO4, filtered and concentrated in vacuum. The
product was purified by flash column chromatography on silica gel with n-pentane/ethyl acetate
as eluent to give the product 3a (0.49 g, 1.34 mmol, 43%).
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To a round-bottom flask were added unactivated alkyl bromides 1a (1.0 g, 3.15 mmol, 1.0
equiv), boron reagent 4 (6.30 mmol, 2.0 equiv), Bis(benzonitrile)palladium(II) chloride (0.157
mmol, 5 mol %), PPh3 (0.315 mmol, 10 mol %) and K2CO3 (4.73 mmol, 1.5 equiv). The reaction
vessel was evacuated and backfilled with Argon for three times, and then injected 15.7 mL DMSO
(0.2 M) into the tube. The reaction mixture was stirred under blue LED irradiation at room
temperature for 24 hours. Then the reaction mixture was quenched with water (30 mL) and
extracted with Et2O (50 mL × 3). The combined organic layers were washed twice with water (30
mL each time) and brine (30 mL), dried over MgSO4. After filtration, the solvents were
evaporated under reduced pressure. The organic extracts was purified by flash column
chromatography on silica gel with n-pentane/ethyl acetate as eluent (to facilitate separation, a
small amount of acetic acid is added in the solvent) to give corresponding product 5a (0.42 g,
1.16 mmol, 37%).
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Light On-off Experiment
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12 samples were conducted under the standard iodization and borylation conditions (six
samples for each of the transformations), except light on-off condition. The reactions were
intermittently exposed to blue-light, and each example was removed at the start and after each
interval. Yields of the 3a and 5a were determined by 1H NMR with 1,3,5-trimethoxybenzene as
an internal standard. It was found that the conversions ceased upon removal from irradiation and
continued upon additional irradiation. We speculated that these systems may be amenable to
photoinduced palladium catalyses which required constant irradiation, rather than just
photoinitiated radical-chain processes.
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UV/Vis Absorption Spectra Studies
We measured UV/Vis absorption spectra to gain more insight into the photoabsorbing Pd
species. To an oven-dried Schlenk tube were added a appropriate amount of samples and
solvents according to the concentrations shown in the pictures. The solutions of the reaction
mixtures were degassed thoroughly by bubbling argon- stream for 20 minutes, and then sealed in
the tubes. Prior to the measurement, the mixtures were kept in the dark unless otherwise noted.
Stern-Volmer Luminescence Quenching Studies.
Stern-Volmer studies were conducted using Pd(PPh3)4 and Pd(PhCN)2Cl2+PPh3 as the
photocatalysts, respectively. 1a and B2(pin)2 were measured to illustrate potential quenching of
the excited Pd species. Prior to the measurement, the solutions of the reaction mixtures were
degassed thoroughly by bubbling argon-stream for 20 minutes. Pd(PPh3)4 sample was irradiated
at 345 nm and emission was measured at 467 nm. Pd(PhCN)2Cl2+PPh3 samples were irradiated at
310 nm and emission was measured at 397 nm. First, the emission spectra of a 1.0×10-3 M
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solution of Pd(PPh3)4 in THF and Pd(PhCN)2Cl2+PPh3 in DMSO were collected, respectively. Then,
the emission spectra of remaining samples was collected.
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Characterization Data of Products 3a - 3p, 5a - 5l, 6, 8, 10 and 11.20
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3-(iodomethyl)-1-tosylpyrrolidine (3a). The product 3a was obtained in 73% yield (53.3 mg,
0.146 mmol, colorless oil); Rf = 0.40 (hexane:ethyl acetate 5:1); 1H NMR (400 MHz, Chloroform-d)
δ 7.79 – 7.67 (m, 2H), 7.39 – 7.30 (m, 2H), 3.50 – 3.35 (m, 2H), 3.30 – 3.19 (m, 1H), 3.09 – 2.93 (m,
3H), 2.44 (s, 3H), 2.43 – 2.35 (m, 1H), 2.08 – 1.96 (m, 1H), 1.61 – 1.49 (m, 1H); 13C{1H} NMR (101
MHz, Chloroform-d) δ 143.6, 133.3, 129.7, 127.5, 53.6, 47.4, 41.2, 32.0, 21.5, 7.2; HRMS (ESI-TOF)
m/z: [M + Na]+ Calcd for C12H16INO2NaS 387.9836, Found 387.9839.
3-(iodomethyl)-1-tosylpiperidine (3b). The product 3b was obtained in 53% yield (40.2 mg,
0.106 mmol, yellow oil); Rf = 0.40 (hexane:ethyl acetate 5:1); 1H NMR (400 MHz, Chloroform-d) δ
7.68 – 7.62 (m, 2H), 7.38 – 7.30 (m, 2H), 3.75 – 3.66 (m, 1H), 3.56 – 3.48 (m, 1H), 3.17 – 2.98 (m,
2H), 2.44 (s, 3H), 2.42 – 2.33 (m, 1H), 2.23 – 2.14 (m, 1H), 1.87 – 1.57 (m, 4H), 1.12 – 0.99 (m, 1H);
13C{1H} NMR (101 MHz, Chloroform-d) δ 143.5, 133.2, 129.6, 127.6, 51.6, 46.4, 37.4, 30.4, 23.8,
21.5, 9.0; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C13H18INO2NaS 401.9995, Found 401.9993.
3-(1-iodoethyl)-1-tosylpyrrolidine (3c). The product 3c was obtained in 66% yield (50.0 mg,
0.132 mmol, yellow oil); The diastereomer ratio of 3c around C3 and C6 on the pyrrolidine ring
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was determined by H NMR analysis (61:39); Rf = 0.40 (hexane:ethyl acetate 5:1); H NMR (400
MHz, Chloroform-d) δ 7.79 – 7.65 (m, 2H), 7.39 – 7.30 (m, 2H), 4.08 – 3.90 (m, 1H), 3.62 – 3.33 (m,
2H), 3.32 – 3.14 (m, 1H), 2.99 – 2.83 (m, 1H), 2.44 (s, 3H), 2.23 – 1.94 (m, 2H), 1.89 – 1.80 (m, 3H),
1.67 – 1.38 (m, 1H); 13C{1H} NMR (101 MHz, Chloroform-d) δ 143.5, 133.3, 129.6, 127.5, 54.6,
48.3, 48.2, 30.3, 29.6, 27.2, 21.5; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C13H18INO2NaS
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401.9995, Found 401.9995.
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3-(iodomethyl)-3-methyl-1-tosylpyrrolidine (3d). The product 3d was obtained in 54% yield
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(40.9 mg, 0.108 mmol, yellow oil); Rf = 0.40 (hexane:ethyl acetate 5:1); H NMR (400 MHz,
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Chloroform-d) δ 7.76 – 7.67 (m, 2H), 7.38 – 7.30 (m, 2H), 3.40 – 3.27 (m, 2H), 3.23 – 3.18 (m, 1H),
3.11 – 3.02 (m, 3H), 2.44 (s, 3H), 1.87 – 1.65 (m, 2H), 1.05 (s, 3H); 13C{1H} NMR (101 MHz,
Chloroform-d) δ 143.5, 133.5, 129.6, 127.3, 58.1, 46.8, 42.4, 36.9, 24.6, 21.4, 17.4; HRMS
(ESI-TOF) m/z: [M + Na]+ Calcd for C13H18INO2NaS 401.9995, Found 401.9995.
3-(iodomethyl)-4-methyl-1-tosylpyrrolidine (3e). The product 3e was obtained in 67% yield
(50.8 mg, 0.134 mmol, colorless oil); The diastereomer ratio of 3e around C3 and C4 on the
pyrrolidine ring was determined by 1H NMR analysis (76:24); Rf = 0.40 (hexane:ethyl acetate 5:1);
1H NMR (400 MHz, Chloroform-d) δ 7.75 – 7.69 (m, 2H), 7.37 – 7.31 (m, 2H), 3.63 – 3.35 (m, 2H),
3.23 – 2.81 (m, 4H), 2.50 – 1.77 (m, 5H), 1.06 – 0.70 (m, 3H); 13C{1H} NMR (101 MHz,
Chloroform-d) δ 143.5, 133.8, 129.7, 127.4, 54.4, 51.8, 45.2, 36.1, 21.5, 12.4, 2.7; HRMS (ESI-TOF)
m/z: [M + Na]+ Calcd for C13H18INO2NaS 401.9995, Found 401.9994.
Dibenzyl 3-(iodomethyl)cyclopentane-1,1-dicarboxylate (3f). The product 3f was obtained in
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56% yield (53.5 mg, 0.112 mmol, colorless oil); Rf = 0.50 (hexane:ethyl acetate 15:1); H NMR
(400 MHz, Chloroform-d) δ 7.33 – 7.20 (m, 10H), 5.14 – 5.06 (m, 4H), 3.22 – 3.08 (m, 2H), 2.61 –
2.49 (m, 1H), 2.45 – 2.17 (m, 3H), 2.02 – 1.83 (m, 2H), 1.48 – 1.32 (m, 1H); 13C{1H} NMR (101 MHz,
Chloroform-d) δ 171.7, 135.3, 128.5, 128.2, 127.9, 67.1, 60.3, 41.9, 40.8, 33.7, 32.6, 11.1; HRMS
(ESI-TOF) m/z: [M + Na]+ Calcd for C22H23IO4Na 501.0533, Found 501.0530.
2-benzyl-3-(iodomethyl)tetrahydrofuran (3g). The product 3g was obtained in 66% yield
(39.9 mg, 0.132 mmol, colorless oil); The diastereomer ratio of 3g around C2 and C3 on the
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tetrahydrofuran ring was determined by 1H NMR analysis (86:14); Rf = 0.40 (hexane:ethyl acetate
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30:1);1H NMR (400 MHz, Chloroform-d) δ 7.42 – 7.14 (m, 5H), 3.95 – 3.69 (m, 3H), 3.12 – 2.78 (m,
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4H), 2.30 – 2.01 (m, 2H), 1.71 (dt, J = 12.5, 6.6 Hz, 1H); C{1H} NMR (101 MHz, Chloroform-d) δ
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138.0, 129.2, 128.4, 126.4, 84.5, 66.5, 46.1, 40.8, 34.1, 9.2; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd
for C12H15IONa 325.0060, Found 325.0056.
2-((benzyloxy)methyl)-5-ethoxy-3-(iodomethyl)tetrahydrofuran (3h). The product 3h was
obtained in 63% yield (47.4 mg, 0.126 mmol, colorless oil); The diastereomer ratio of 3h around
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C2 and C3 on the tetrahydrofuran ring was determined by H NMR analysis (86:14); Rf = 0.50
(hexane:ethyl acetate 20:1); 1H NMR (400 MHz, Chloroform-d) δ 7.41 – 7.23 (m, 5H), 5.25 – 5.03
(m, 1H), 4.65 – 4.55 (m, 2H), 4.04 – 2.93 (m, 7H), 2.55 – 1.72 (m, 3H), 1.24 – 1.09 (m, 3H); 13C{1H}
NMR (101 MHz, Chloroform-d) δ 138.06, 138.05, 128.34, 128.28, 127.63, 127.60, 127.59, 127.58,
103.4, 103.3, 82.9, 82.2, 73.6, 73.4, 73.3, 71.4, 62.8, 62.4, 43.0, 42.7, 41.1, 40.4, 15.2, 15.1, 9.8,
9.2; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C15H21IO3Na 399.0428, Found 399.0422.
2-benzyl-4-(iodomethyl)tetrahydrofuran (3i). The product 3i was obtained in 55% yield
(33.2 mg, 0.110 mmol, colorless oil); The diastereomer ratio of 3i around C3 and C5 on the
tetrahydrofuran ring was determined by 1H NMR analysis (82:18); Rf = 0.40 (hexane:ethyl acetate
30:1); 1H NMR (400 MHz, Chloroform-d) δ 7.77 – 7.13 (m, 5H), 4.28 – 4.10 (m, 1H), 4.09 – 3.83 (m,
1H), 3.64 – 3.40 (m, 1H), 3.30 – 3.09 (m, 2H), 3.01 – 2.85 (m, 1H), 2.83 – 2.69 (m, 1H), 2.68 – 2.55
(m, 1H), 2.23 – 1.67 (m, 2H), 1.58 – 0.84 (m, 1H); 13C{1H} NMR (101 MHz, Chloroform-d) δ 138.3,
129.2, 128.4, 126.3, 79.6, 73.6, 41.9, 41.8, 38.4, 8.7; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for
C12H15IONa 325.0060, Found 325.0057.
4-(iodomethyl)-2-(4-methoxyphenyl)tetrahydrofuran (3j). The product 3j was obtained in
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25% yield (15.9 mg, 0.050 mmol, colorless oil); The diastereomer ratio of 3j around C3 and C5 on
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the tetrahydrofuran ring was determined by H NMR analysis (86:14); Rf = 0.50 (hexane:ethyl
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acetate 30:1); 1H NMR (400 MHz, Chloroform-d) δ 7.37 – 7.15 (m, 2H), 7.00 – 6.79 (m, 2H), 4.99 (t,
J = 7.2 Hz, 1H), 4.35 – 4.16 (m, 1H), 3.79 (s, 3H), 3.63 – 3.51 (m, 1H), 3.38 – 3.15 (m, 2H), 2.89 –
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2.66 (m, 1H), 2.17 – 1.98 (m, 2H); C{1H} NMR (101 MHz, Chloroform-d) δ 158.9, 134.5, 126.8,
113.7, 79.9, 74.1, 55.3, 42.0, 41.6, 8.5; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C12H15IO2Na
341.0009, Found 341.0004.
2-benzyl-3-(iodomethyl)hexahydrofuro[2,3-b]furan (3k). The product 3k was obtained in
59% yield (40.6 mg, 0.118 mmol, colorless oil); The diastereomer ratio of 3k around C3 and C4 on
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the tetrahydrofuran ring was determined by H NMR analysis (92:8), and the diastereomer ratio
of 3k around C2 and C3 on the tetrahydrofuran ring was over 95:5; Rf = 0.40 (hexane:ethyl acetate
20:1); 1H NMR (400 MHz, Chloroform-d) δ 7.35 – 7.19 (m, 5H), 5.68 – 5.60 (m, 1H), 3.99 – 3.65 (m,
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3H), 3.09 – 2.86 (m, 4H), 2.63 – 2.52 (m, 1H), 2.06 – 1.91 (m, 1H), 1.79 – 1.63 (m, 2H); C{1H}
NMR (101 MHz, Chloroform-d) δ 137.2, 129.4, 128.4, 126.6, 107.7, 84.1, 66.5, 51.0, 49.9, 40.3,
32.5, 7.8; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C14H17IO2Na 367.0165, Found 367.0163.
3-(iodomethyl)-2-phenylhexahydrofuro[2,3-b]furan (3l). The product 3l was obtained in
72% yield (47.5 mg, 0.144 mmol, colorless oil); The diastereomer ratio of 3l around C3 and C4 on
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the tetrahydrofuran ring was determined by H NMR analysis (81:19); Rf = 0.40 (hexane:ethyl
acetate 25:1); 1H NMR (400 MHz, Chloroform-d) δ 7.40 – 7.27 (m, 5H), 5.97 – 5.87 (m, 1H), 4.60 –
4.41 (m, 1H), 4.10 – 3.91 (m, 2H), 3.22 – 2.49 (m, 4H), 2.17 – 1.84 (m, 2H); 13C{1H} NMR (101 MHz,
Chloroform-d) δ 138.8, 128.6, 128.5, 126.4, 107.6, 83.5, 68.9, 54.3, 47.9, 24.8, 0.1; HRMS
(ESI-TOF) m/z: [M + Na]+ Calcd for C13H15IO2Na 353.0009, Found 353.0004.
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3-(iodomethyl)-1-tosyloctahydro-1H-indole (3m). The product 3m was obtained in 31%
yield (26.0 mg, 0.062 mmol, colorless oil); The diastereomer ratio of 3m around C2 and C3 on the
pyrrolidine ring was determined by 1H NMR analysis (>95:5); Rf = 0.40 (hexane:ethyl acetate 4:1);
1H NMR (400 MHz, Chloroform-d) δ 7.74 – 7.67 (m, 2H), 7.37 – 7.31 (m, 2H), 3.65 – 3.55 (m, 1H),
3.36 – 3.30 (m, 1H), 3.25 – 3.15 (m, 1H), 3.06 – 2.90 (m, 2H), 2.63 – 2.54 (m, 1H), 2.45 (s, 3H),
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2.07 – 1.95 (m, 2H), 1.84 – 1.74 (m, 1H), 1.64 – 1.43 (m, 4H), 1.24 – 1.10 (m, 2H); C{1H} NMR
(101 MHz, Chloroform-d) δ 143.5, 133.5, 129.7, 127.6, 61.0, 52.9, 43.6, 42.0, 28.5, 24.1, 21.5,
21.3, 20.0, 1.9; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C16H22INO2NaS 442.0308, Found
442.0305.
4-iodo-1-tosyloctahydro-1H-indole (3n). The product 3n was obtained in 33% yield (26.7 mg,
0.066 mmol, yellow oil); The diastereomer ratio of 3n around C2 and C3 on the pyrrolidine ring
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was determined by H NMR analysis (＞95:5); Rf = 0.30 (hexane:ethyl acetate 4:1); H NMR (400
MHz, Chloroform-d) δ 7.76 – 7.67 (m, 2H), 7.37 – 7.28 (m, 2H), 4.42 – 4.32 (m, 1H), 3.71 – 3.62 (m,
1H), 3.62 – 3.50 (m, 1H), 3.32 – 3.21 (m, 1H), 2.44 (s, 3H), 2.35 – 2.22 (m, 1H), 2.15 – 1.74 (m, 5H),
1.73 – 1.56 (m, 3H); 13C{1H} NMR (101 MHz, Chloroform-d) δ 143.4, 134.1, 129.7, 127.4, 58.9,
49.5, 47.1, 34.9, 32.3, 28.7, 28.6, 21.9, 21.5; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for
C15H20INO2NaS 428.0152, Found 428.0149.
3-benzylidene-1-tosylpyrrolidine (3o). The product 3o was obtained in 21% yield (13.2 mg,
0.042 mmol, white solid); The crude product 3o is a diastereomixture in term of the new formed
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double bond; Rf = 0.30 (hexane:ethyl acetate 25:1); H NMR (400 MHz, Chloroform-d) δ 7.82 –
7.66 (m, 2H), 7.43 – 7.27 (m, 4H), 7.25 – 7.09 (m, 3H), 6.40 – 6.23 (m, 1H), 4.14 – 3.92 (m, 2H),
3.45 – 3.23 (m, 2H), 2.80 – 2.63 (m, 2H), 2.47 – 2.37 (m, 3H). 13C{1H} NMR (101 MHz,
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Chloroform-d) δ 143.73, 143.65, 137.0, 136.77, 136.76, 136.5, 132.8, 132.4, 129.70, 129.69,
128.5, 128.4, 128.1, 127.92, 127.90, 127.7, 126.9, 126.8, 123.3, 122.6, 53.7, 50.4, 48.5, 46.7, 33.7,
29.8, 21.5, 21.5; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C18H20NO2S 314.1209, Found 314.1204.
3-(propan-2-ylidene)-1-tosylpyrrolidine (3p). The product 3p was obtained in 59% yield
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(31.3 mg, 0.118 mmol, colorless oil); Rf = 0.50 (hexane:ethyl acetate 20:1); H NMR (400 MHz,
Chloroform-d) δ 7.77 – 7.69 (m, 2H), 7.38 – 7.30 (m, 2H), 3.76 – 3.66 (m, 2H), 3.26 – 3.22 (m, 2H),
2.43 (s, 3H), 2.42 – 2.37 (m, 2H), 1.60 - 1.55 (m, 6H); 13C{1H} NMR (101 MHz, Chloroform-d) δ
143.5, 132.3, 129.5, 127.9, 127.6, 124.1, 50.5, 48.2, 28.9, 21.4, 20.8, 20.7; HRMS (ESI-TOF) m/z:
[M + H]+ Calcd for C14H20NO2S 266.1209, Found 266.1204.
3-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)-1-tosylpyrrolidine (5a). The product
5a was obtained in 64% yield (46.7 mg, 0.128 mmol, colorless oil); Rf = 0.30 (hexane:ethyl acetate
5:1); 1H NMR (400 MHz, Chloroform-d) δ 7.75 – 7.67 (m, 2H), 7.35 – 7.29 (m, 2H), 3.57 – 3.45 (m,
1H), 3.39 – 3.30 (m, 1H), 3.25 – 3.15 (m, 1H), 2.77 – 2.69 (m, 1H), 2.43 (s, 3H), 2.23 – 2.10 (m, 1H),
2.00 – 1.89 (m, 1H), 1.40 – 1.29 (m, 1H), 1.21 (s, 12H), 0.77 – 0.75 (m, 2H); 13C{1H} NMR (101
MHz, Chloroform-d) δ 143.1, 134.0, 129.5, 127.5, 83.2, 55.0, 47.7, 34.8, 33.5, 24.75, 24.71, 21.5
(The carbon directly attached to the boron atom was not detected); HRMS (ESI-TOF) m/z: [M +
Na]+ Calcd for C18H28BNO4NaS 388.1724; Found 388.1721.
3-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)-1-tosylpiperidine
(5b).
The
product 5b was obtained in 46% yield (11.2 mg, 0.030 mmol, colorless oil); Rf = 0.30
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(hexane:ethyl acetate 5:1); H NMR (400 MHz, Chloroform-d) δ 7.67 – 7.61 (m, 2H), 7.34 – 7.29
(m, 2H), 3.72 – 3.58 (m, 2H), 2.43 (s, 3H), 2.29 – 2.16 (m, 1H), 2.01 – 1.89 (m, 1H), 1.89 – 1.80 (m,
1H), 1.79 – 1.53 (m, 3H), 1.24 (s, 12H), 0.92 – 0.77 (m, 1H), 0.75 – 0.60 (m, 2H); 13C{1H} NMR (101
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MHz, Chloroform-d) δ 143.1, 133.7, 129.4, 127.6, 83.1, 53.4, 46.3, 32.3, 32.0, 24.73, 24.72, 21.4,
16.1; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C19H30BNO4NaS 402.1881; Found 402.1883.
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3-methyl-4-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)-1-tosylpyrrolidine
(5c).
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The product 5c was obtained in 51% yield (38.7 mg, 0.102 mmol, colorless oil); The diastereomer
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ratio of 5c around C3 and C4 on the pyrrolidine ring was determined by H NMR analysis (71:29);
Rf = 0.30 (hexane:ethyl acetate 5:1); 1H NMR (400 MHz, Chloroform-d) δ 7.74 – 7.66 (m, 2H), 7.35
– 7.28 (m, 2H), 3.65 – 3.31 (m, 2H), 3.02 – 2.74 (m, 2H), 2.43 (s, 3H), 2.24 – 2.12 (m, 1H), 1.71 –
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1.55 (m, 1H), 1.22 (s, 12H), 0.91 – 0.87 (m, 1H), 0.72 – 0.66 (m, 3H), 0.60 – 0.50 (m, 1H); C{1H}
NMR (101 MHz, Chloroform-d) δ 143.1, 143.1, 134.2, 134.1, 129.5, 129.5, 127.4, 127.4, 83.3, 83.2,
54.8, 54.8, 54.4, 53.2, 41.8, 41.0, 37.7, 36.2, 24.8, 24.74 , 24.72 , 21.5, 15.5, 13.0 (The carbon
directly attached to the boron atom was not detected); HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for
C19H30BNO4NaS 402.1881; Found 402.1881.
3-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)-1-tosyloctahydro-1H-indole (5d).
The product 5d was obtained in 35% yield (29.4 mg, 0.070 mmol, colorless oil); The diastereomer
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ratio of 5d around C3 on the pyrrolidine ring was determined by H NMR analysis (80:20); Rf =
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0.30 (hexane:ethyl acetate 4:1); H NMR (400 MHz, Chloroform-d) δ 7.76 – 7.66 (m, 2H), 7.36 –
7.27 (m, 2H), 3.64 – 3.49 (m, 1H), 3.36 – 3.26 (m, 1H), 3.17 – 3.04 (m, 1H), 2.43 (s, 3H), 1.90 –
1.78 (m, 1H), 1.80 – 1.58 (m, 3H), 1.53 – 1.39 (m, 4H), 1.21 (s, 12H), 1.16 – 1.04 (m, 2H), 0.77 –
0.59 (m, 2H); 13C{1H} NMR (101 MHz, Chloroform-d) δ 143.0, 134.0, 129.5, 127.7, 83.2, 61.1, 54.7,
42.3, 36.4, 28.6, 24.7, 24.5, 22.3, 21.5, 20.2 (The carbon directly attached to the boron atom was
not detected); HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C22H34BNO4NaS 442.2194; Found
442.2194.
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2-((5-(4-methoxyphenyl)tetrahydrofuran-3-yl)methyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborola
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ne (5e). The product 5e was obtained in 34% yield (21.6 mg, 0.068 mmol, colorless oil); The
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diastereomer ratio of 5e around C3 and C5 on the tetrahydrofuran ring was determined by H
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NMR analysis (88:12); Rf = 0.30 (hexane:ethyl acetate 30:1); H NMR (400 MHz, Chloroform-d) δ
7.29 – 7.21 (m, 2H), 6.90 – 6.79 (m, 2H), 4.94 (t, J = 7.0 Hz, 1H), 4.27 – 4.18 (m, 1H), 3.79 (s, 3H),
3.46 – 3.38 (m, 1H), 2.57 – 2.48 (m, 1H), 2.08 – 1.98 (m, 1H), 1.96 – 1.89 (m, 1H), 1.24 (s, 12H),
0.96 – 0.94 (m, 2H); 13C{1H} NMR (101 MHz, Chloroform-d) δ 158.7, 135.9, 127.0, 113.6, 83.1,
79.8, 75.9, 55.2, 42.7, 34.7, 24.8 (The carbon directly attached to the boron atom was not
detected); HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C18H27BO4Na 341.1895; Found 341.1895.
2-((2-((benzyloxy)methyl)-5-ethoxytetrahydrofuran-3-yl)methyl)-4,4,5,5-tetramethyl-1,3,2-d
ioxaborolane (5f). The product 5f was obtained in 55% yield (41.4 mg, 0.110 mmol, colorless oil);
The diastereomer ratio of 5f around C2 and C3 on the tetrahydrofuran ring was determined by 1H
NMR analysis (76:24); The product 5f is a diastereomixture in term of the acetal moiety (C5) due
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to the stereochemistry of the starting material; Rf = 0.40 (hexane:ethyl acetate 20:1); H NMR
(400 MHz, Chloroform-d) δ 7.39 – 7.27 (m, 5H), 5.23 – 4.87 (m, 1H), 4.66 – 4.28 (m, 2H), 3.87 –
3.30 (m, 5H), 2.46 – 1.90 (m, 2H), 1.69 – 1.47 (m, 1H), 1.28 – 0.75 (m, 17H); 13C{1H} NMR (101
MHz, Chloroform-d) δ 138.5, 138.4, 128.3, 128.0, 127.7, 127.6, 127.4, 127.4, 103.8, 103.6, 86.1,
83.9, 83.2, 83.1, 73.8, 73.3, 73.2, 71.2, 63.0, 62.2, 41.1, 40.9, 35.9, 35.2, 24.8, 24.7, 15.3, 15.2
(The carbon directly attached to the boron atom was not detected); HRMS (ESI-TOF) m/z: [M +
Na]+ Calcd for C21H33BO5Na 399.2313, Found 399.2309.
4,4,5,5-tetramethyl-2-((2-phenylhexahydrofuro[2,3-b]furan-3-yl)methyl)-1,3,2-dioxaborolan
e (5g). The product 5g was obtained in 42% yield (27.7 mg, 0.084 mmol, colorless oil); The
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diastereomer ratio of 5g around C3 on the tetrahydrofuran ring was determined by H NMR
analysis (>95:5); Rf = 0.40 (hexane:ethyl acetate 20:1); 1H NMR (400 MHz, Chloroform-d) δ 7.42 –
7.27 (m, 5H), 5.76 (d, J = 5.5 Hz, 1H), 4.35 (d, J = 9.4 Hz, 1H), 4.08 – 4.01 (m, 2H), 2.64 – 2.56 (m,
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1H), 1.99 – 1.83 (m, 3H), 1.23 – 1.16 (m, 12H), 1.08 – 0.95 (m, 1H), 0.89 – 0.80 (m, 1H).; C{1H}
NMR (101 MHz, Chloroform-d) δ 140.2, 128.3, 127.8, 126.4, 108.4, 87.7, 83.3, 66.8, 51.2, 48.4,
32.1, 24.9 (The carbon directly attached to the boron atom was not detected); HRMS (ESI-TOF)
m/z: [M + Na]+ Calcd for C19H27BO4Na 353.1895; Found 353.1896.
Dibenzyl
3-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)cyclopentane-1,1-dicarboxylate (5h). The
product 5h was obtained in 57% yield (54.5 mg, 0.114 mmol, colorless oil); Rf = 0.50
(hexane:ethyl acetate 15:1); 1H NMR (400 MHz, Chloroform-d) δ 7.41 – 7.15 (m, 10H), 5.28 – 4.92
(m, 4H), 2.59 – 2.51 (m, 1H), 2.38 – 2.30 (m, 1H), 2.23 – 2.08 (m, 2H), 1.96 – 1.86 (m, 1H), 1.79 –
1.67 (m, 1H), 1.26 (s, 1H), 1.21 (s, 12H), 0.94 – 0.79 (m, 2H); 13C{1H} NMR (101 MHz,
Chloroform-d) δ 172.4, 135.7, 128.4, 128.1, 127.9, 83.0, 66.9, 60.3, 42.9, 35.9, 34.3, 34.0, 24.8
(The carbon directly attached to the boron atom was not detected); HRMS (ESI-TOF) m/z: [M +
Na]+ Calcd for C28H35BO6Na 501.2420; Found 501.2419.
3-((5,5-dimethyl-1,3,2-dioxaborinan-2-yl)methyl)-1-tosylpyrrolidine (5i). The product 5i was
obtained in 52% yield (36.5 mg, 0.104 mmol, colorless oil); Rf = 0.30 (hexane:ethyl acetate 5:1);
1H NMR (400 MHz, Chloroform-d) δ 7.75 – 7.66 (m, 2H), 7.35 – 7.28 (m, 2H), 3.55 (s, 4H), 3.53 –
3.47 (m, 1H), 3.37 – 3.29 (m, 1H), 3.22 – 3.14 (m, 1H), 2.76 – 2.68 (m, 1H), 2.43 (s, 3H), 2.20 –
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2.09 (m, 1H), 1.97 – 1.88 (m, 1H), 1.37 – 1.25 (m, 1H), 0.93 (s, 6H), 0.72 – 0.65 (m, 2H); C{1H}
NMR (101 MHz, Chloroform-d) δ 143.0, 134.1, 129.5, 127.4, 71.9, 55.1, 47.7, 34.8, 33.7, 31.5,
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21.7, 21.5 (The carbon directly attached to the boron atom was not detected); HRMS (ESI-TOF)
m/z: [M + H]+ Calcd for C17H27BNO4S 352.1748, Found 352.1743.
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(1-tosylpyrrolidin-3-yl)methanol (5j). The product 5j was obtained in 55% yield (28.1 mg,
0.110 mmol, colorless oil); Rf = 0.30 (hexane:ethyl acetate 1:1); 1H NMR (400 MHz, Chloroform-d)
δ 7.78 – 7.66 (m, 2H), 7.38 – 7.30 (m, 2H), 3.52 – 3.40 (m, 2H), 3.37 – 3.28 (m, 2H), 3.24 – 3.14 (m,
1H), 3.11 – 3.04 (m, 1H), 2.44 (s, 3H), 2.37 – 2.26 (m, 1H), 1.96 – 1.85 (m, 1H), 1.68 (s, 1H), 1.63 –
1.53 (m, 1H); 13C{1H} NMR (101 MHz, Chloroform-d) δ 143.5, 133.4, 129.6, 127.6, 64.1, 50.3, 47.3,
40.7, 27.6, 21.5; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C12H18NO3S 256.1002, Found 256.0996.
1-tosyl-3-vinylpyrrolidine (5k). The product 5k was obtained in 76% yield (38.2 mg, 0.152
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mmol, colorless oil); Rf = 0.50 (hexane:ethyl acetate 20:1); H NMR (400 MHz, Chloroform-d) δ
7.78 – 7.64 (m, 2H), 7.41 – 7.30 (m, 2H), 5.65 – 5.54 (m, 1H), 5.05 – 4.91 (m, 2H), 3.49 – 3.43 (m,
1H), 3.40 – 3.34 (m, 1H), 3.28 – 3.20 (m, 1H), 2.98 – 2.90 (m, 1H), 2.72 – 2.61 (m, 1H), 2.43 (s, 3H),
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2.00 – 1.89 (m, 1H), 1.63 – 1.51 (m, 1H); C{1H} NMR (101 MHz, Chloroform-d) δ 143.3, 137.4,
133.7, 129.5, 127.3, 115.7, 52.4 , 47.3, 42.3, 31.4, 21.4; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
C13H18NO2S 252.1053, Found 252.1050.
3-(prop-1-en-2-yl)-1-tosylpyrrolidine (5l). The product 5l was obtained in 64% yield (33.9
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mg, 0.128 mmol, colorless oil); Rf = 0.50 (hexane:ethyl acetate 20:1); H NMR (400 MHz,
Chloroform-d) δ 7.80 – 7.67 (m, 2H), 7.43 – 7.30 (m, 2H), 4.79 – 4.59 (m, 2H), 3.53 – 3.35 (m, 2H),
3.28 – 3.19 (m, 1H), 3.06 – 2.97 (m, 1H), 2.68 – 2.54 (m, 1H), 2.43 (s, 3H), 1.98 – 1.89 (m, 1H),
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1.71 – 1.58 (m, 4H); C{1H} NMR (101 MHz, Chloroform-d) δ 143.6, 143.3, 133.8, 129.5, 127.3,
110.7, 51.4, 47.6, 45.0 , 29.8, 21.4, 20.9; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for C14H20NO2S
266.1209, Found 266.1205.
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3-(3,3-diphenylallyl)-1-tosylpyrrolidine (6). The product 6 were obtained in 67% yield (55.9
mg, 0.134 mmol, colorless oil) and 52% yield (43.4 mg, 0.104 mmol, colorless oil), respectively; Rf
= 0.50 (hexane:ethyl acetate 15:1); 1H NMR (400 MHz, Chloroform-d) δ 7.7 – 7.6 (m, 2H), 7.4 – 7.2
(m, 8H), 7.2 – 7.1 (m, 2H), 7.1 – 7.1 (m, 2H), 5.9 (t, J = 7.3 Hz, 1H), 3.5 – 3.4 (m, 1H), 3.3 – 3.1 (m,
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2H), 2.8 – 2.7 (m, 1H), 2.4 (s, 3H), 2.2 – 2.0 (m, 3H), 2.0 – 1.8 (m, 1H), 1.5 – 1.3 (m, 1H); C{1H}
NMR (101 MHz, Chloroform-d) δ 143.3, 143.2, 142.2, 139.7, 133.9, 129.7, 129.6, 128.3, 128.1,
127.5, 127.13, 127.11, 127.08, 126.3, 52.9, 47.4, 39.2, 32.8, 30.9, 21.5; HRMS (ESI-TOF) m/z: [M +
H]+ Calcd for C26H28NO2S 418.1835, Found 418.1835.
3-(2-(3,4-dihydronaphthalen-1-yl)ethyl)-1-tosylpyrrolidine (8). The product 8 were
obtained in 27% yield (20.6 mg, 0.054 mmol, colorless oil) and 35% yield (26.7 mg, 0.070 mmol,
colorless oil), respectively; Rf = 0.50 (hexane:ethyl acetate 10:1); 1H NMR (400 MHz, Chloroform-d)
δ 7.8 – 7.7 (m, 2H), 7.4 – 7.3 (m, 2H), 7.2 – 7.1 (m, 4H), 5.8 (t, J = 4.6 Hz, 1H), 3.5 – 3.4 (m, 1H),
3.4 – 3.3 (m, 1H), 3.2 – 3.1 (m, 1H), 2.8 – 2.8 (m, 1H), 2.7 – 2.6 (m, 2H), 2.4 (s, 3H), 2.4 – 2.3 (m,
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2H), 2.3 – 2.2 (m, 2H), 2.1 – 2.0 (m, 1H), 2.0 – 1.9 (m, 1H), 1.5 – 1.3 (m, 3H); C{1H} NMR (101
MHz, Chloroform-d) δ 143.2, 136.8, 135.7, 134.4, 133.9, 129.6, 127.7, 127.5, 126.7, 126.3, 125.2,
122.4, 53.2, 47.5, 38.5, 31.8, 31.4, 31.2, 28.3, 23.0, 21.5; HRMS (ESI-TOF) m/z: [M + H]+ Calcd for
C23H28NO2S 382.1835, Found 382.1833.
3-(4-iodobut-1-en-1-yl)-2-phenethyltetrahydrofuran (10). The product 10 was obtained in
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19% yield (13.5 mg, 0.038 mmol, colorless oil); The E/Z ratio of 10 was determined by H NMR
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analysis (83:17); Rf = 0.40 (hexane:ethyl acetate 30:1); H NMR (600 MHz, Chloroform-d) δ 7.3 –
7.2 (m, 2H), 7.2 – 7.1 (m, 3H), 5.5 – 5.4 (m, 2H), 4.0 – 3.8 (m, 2H), 3.5 – 3.4 (m, 1H), 3.2 – 3.1 (m,
2H), 2.9 – 2.8 (m, 1H), 2.7 – 2.3 (m, 4H), 2.2 – 2.1 (m, 1H), 2.0 – 1.8 (m, 1H), 1.8 – 1.7 (m, 2H);
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13C{1H} NMR (151 MHz, Chloroform-d) δ 142.2, 133.4, 129.9, 128.4, 128.3, 125.7, 83.0, 67.0, 48.7,
36.3, 35.7, 33.4, 32.8, 5.9; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C16H21IONa 379.0529, Found
379.0527.
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4,4,5,5-tetramethyl-2-(4-(2-phenethyltetrahydrofuran-3-yl)but-3-en-1-yl)-1,3,2-dioxaborol
ane (11). The product 11 was obtained in 22% yield (15.7 mg, 0.044 mmol, colorless oil); The E/Z
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ratio of 11 was determined by H NMR analysis (85:15); Rf = 0.30 (hexane:ethyl acetate 15:1); H
NMR (600 MHz, Chloroform-d) δ 7.3 – 7.2 (m, 2H), 7.2 – 7.1 (m, 3H), 5.6 – 5.4 (m, 1H), 5.3 – 5.1
(m, 1H), 3.9 – 3.8 (m, 2H), 3.5 – 3.4 (m, 1H), 2.9 – 2.8 (m, 1H), 2.7 – 2.6 (m, 1H), 2.4 – 2.2 (m, 1H),
2.1 – 2.1 (m, 3H), 1.9 – 1.8 (m, 1H), 1.8 – 1.7 (m, 2H), 1.2 – 1.2 (m, 12H), 0.9 – 0.8 (m, 2H); 13C{1H}
NMR (151 MHz, Chloroform-d) δ 142.4, 133.8, 128.99, 128.98, 128.4, 128.2, 125.6, 83.2, 82.9,
67.0, 48.7, 35.7, 33.7, 32.8, 26.7, 24.8, 22.1; HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for
C22H33BO3Na 379.2415, Found 379.2412.
Supporting Information
Instrumentation, the graphics of carbon atom numbers in characterization data, optimization of
reaction conditions. UV/Vis absorption spectra studies, Stern-Volmer luminescence quenching
studies and NMR Spectra
AUTHOR INFORMATION
Corresponding Author
Yong-Min Liang − Lanzhou University, Lanzhou, P.R.
China; orcid.org/0000-0001-8280-8211;
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Email: liangym@lzu.edu.cn
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Acknowledgment
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Financial support was received from the National Natural Science Foundation of China
(NSF21532001, NSF21772075) and the “111” project, and we would like to thank ACS
CHEMWORX (https://es.acschemworx.acs.org/en/) for providing linguistic assistance during the
preparation of this manuscript.
Reference
(1) (a) You, W.; Brown, M. K. Catalytic Enantioselective Diarylation of Alkenes. J. Am. Chem. Soc.
2015, 137, 14578-14581; (b) Bardagi, J.; Vaillard, V.; Rossi, R. Encyclopedia of Radicals in
Chemistry, Biology and Materials. 2012; (c) Habraken, C. L. Pyrroles. Part two. The Synthesis,
Reactivity, and Physical Properties of Substituted Pyrroles R.A. Jones, ed. John Wiley & Sons, 1992
xv + 628 pp., £157.00 ISBN 0-471-51306-7. 1993, 112, 649-649.
(2) (a) Matteson, D. Boronic Acids: Preparation and Applications in Organic Synthesis and
Medicine. 2006, 305-342; (b) Ye, S.; Xiang, T.; Li, X.; Wu, J. Metal-catalyzed radical-type
transformation of unactivated alkyl halides with C–C bond formation under photoinduced
conditions. Org. Chem. Front. 2019, 6, 2183-2199; (c) Rezazadeh, S.; Devannah, V.; Watson, D. A.
Nickel-Catalyzed C-Alkylation of Nitroalkanes with Unactivated Alkyl Iodides. J. Am. Chem. Soc.
2017, 139, 8110-8113; (d) Wang, S.; Zhang, J.; Kong, L.; Tan, Z.; Bai, Y.; Zhu, G.
Palladium-Catalyzed anti-Selective Fluoroalkylboration of Internal and Terminal Alkynes. Org. Lett.
2018, 20, 5631-5635; (e) Weng, W.-Z.; Liang, H.; Liu, R.-Z.; Ji, Y.-X.; Zhang, B.
Visible-Light-Promoted Manganese-Catalyzed Atom Transfer Radical Cyclization of Unactivated
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The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
Alkyl Iodides. Org. Lett. 2019, 21, 5586-5590; (f) Ollivier, C.; Renaud, P. A Novel Approach for the
Formation of Carbon−Nitrogen Bonds:ꢀ Azidation of Alkyl Radicals with Sulfonyl Azides. J. Am.
Chem. Soc. 2001, 123, 4717-4727.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(3) (a) Cong, H.; Fu, G. C. Catalytic Enantioselective Cyclization/Cross-Coupling with Alkyl
Electrophiles. J. Am. Chem. Soc. 2014, 136, 3788-3791; (b) Sun, Q.; Yoshikai, N. Cobalt-Catalyzed
Tandem Radical Cyclization/C–C Coupling Initiated by Directed C–H Activation. Org. Lett. 2019, 21,
5238-5242; (c) Cui, J.; Wang, H.; Song, J.; Chi, X.; Meng, L.; Liu, Q.; Zhang, D.; Dong, Y.; Liu, H.
Copper(i)-catalyzed 5-exo-trig radical cyclization/borylation of alkyl halides: access to
functionalized pyrrolidine derivatives. Org. Biomol. Chem. 2017, 15, 8508-8512; (d) Xue, W.; Qu,
Z.-W.; Grimme, S.; Oestreich, M. Copper-Catalyzed Cross-Coupling of Silicon Pronucleophiles with
Unactivated Alkyl Electrophiles Coupled with Radical Cyclization. J. Am. Chem. Soc. 2016, 138,
14222-14225; (e) Thapa, S.; Basnet, P.; Giri, R. Copper-Catalyzed Dicarbofunctionalization of
Unactivated Olefins by Tandem Cyclization/Cross-Coupling. J. Am. Chem. Soc. 2017, 139,
5700-5703; (f) Whitewoods, C. D.; Gonçalves, B.; Cheng, J.; Cui, M.; Kennaway, R.; Lee, K.; Bushell,
C.; Yu, M.; Piao, C.; Coen, E. Evolution of carnivorous traps from planar leaves through simple
shifts in gene expression. science 2020, 367, 91-96; (g) Kuang, Y.; Wang, X.; Anthony, D.; Diao, T.
Ni-catalyzed two-component reductive dicarbofunctionalization of alkenes via radical cyclization.
Chem. Commun. 2018, 54, 2558-2561; (h) Ma, J.-W.; Wang, Q.; Wang, X.-G.; Liang, Y.-M.
Palladium-Catalyzed Cascade Difluoroalkylation/Cyclization of N-Propargylamides: Synthesis of
Oxazoles and Oxazolines. J. Org. Chem. 2018, 83, 13296-13307.
(4) (a) Yong, X.; Han, Y.-F.; Li, Y.; Song, R.-J.; Li, J.-H. Alkylarylation of styrenes via direct
C(sp3)–Br/C(sp2)–H functionalization mediated by photoredox and copper cooperative catalysis.
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