Radical Addition Enables 1,2-Aryl Migration from a Vinyl-Substituted All-Carbon Quaternary Center

Article abstract of DOI:10.1002/anie.202010839

An efficient method for photocatalytic perfluoroalkylation of vinyl-substituted all-carbon quaternary centers involving 1,2-aryl migration has been developed. The rearrangement reactions use fac-Ir(ppy)₃, visible light and commercially available fluoroalkyl halides and can generate valuable multisubstituted perfluoroalkylated compounds in a single step that would be challenging to prepare by other methods. Mechanistically, the photoinduced alkyl radical addition to an alkene leads to the migration of a vicinal aryl substituent from its adjacent all-carbon quaternary center with the concomitant generation of a C-radical bearing two electron-withdrawing groups that is further reduced by a hydrogen donor to complete the domino sequence.

Full text of DOI:10.1002/anie.202010839

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
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Accepted Article
Title: 1,2-Aryl Migration of Vinyl-Substituted All-Carbon Quaternary
Centers Enabled by Radical Addition
Authors: Zhuangzhi Shi
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202010839
Link to VoR: https://doi.org/10.1002/anie.202010839

10.1002/anie.202010839
Angewandte Chemie International Edition
Rearrangement
C−N Bond Activation
Radical Addition Enables 1,2-Aryl Migration from Vinyl-Substituted All-
Carbon Quaternary Center
Zexian Li, Minyan Wang, and Zhuangzhi Shi*
Dedicated to the 100th anniversary of the School of Chemistry and Chemical Engineering, Nanjing University
Abstract: An efficient method for photocatalytic perfluoroalkylation
of vinyl-substituted all-carbon quaternary centers involving 1,2-aryl
migration has been developed. The rearrangement reactions use
fac-Ir(ppy)3, visible light and commercially available fluoroalkyl
halides
and
can
generate
valuable
multisubstituted
perfluoroalkylated compounds in a single step that would be
challenging to prepare by other methods. Mechanistically, the
photoinduced alkyl radical addition to an alkene leads to the
migration of a vicinal aryl substituent from its adjacent all-carbon
quaternary center with the concomitant generation of C-radical
bearing two electron-withdrawing groups that is further reduced by
a hydrogen donor to complete the domino sequence.
Rearrangement reactions are among the most attractive
transformations in the field of chemical synthesis, and these
reactions are convenient, efficient and atom-economic
procedures for constructing organic compounds with new
skeletons.[1] Among these reactions, radical-mediated
functionality migration has gained increasing attention.[2]
Radical-induced 1,2-rearrangement is the subject of
considerable interest in this area.[3] The first radical 1,2-
migration in β-aryl carbon-centered radicals, named the
neophyl rearrangement, was discovered by Urry and Kharasch
in 1944.[4] However, the limited substrate scope, slow process
and harsh reaction conditions make it difficult to apply in
organic synthesis.
Figure 1. Radical-induced 1,2-migration in olefins.
olefins bearing adjacent all-carbon quaternary centers can
undergo 1,2-aryl migration through radical addition (Figure 1d).
The installation of a perfluoroalkyl substitution into organic
compounds typically results in great changes in their properties
like the polarity, solubility, conformational behavior, and
metabolic stability.[13] Perfluoroalkylation of alkenes has been
one of the most efficient methods for introducing
perfluoroalkyl substitution into organic molecules.[14] Different
from the reported process, this reaction proceeds through
perfluoroalkyl-radical addition to the olefinic double bonds,
and the adduct radical undergoes 1,2-aryl migration to afford a
translocated C-radical, which is further reduced by a hydrogen
donor.[15] Visible-light photoredox catalysis[16] makes this
strategy possible under mild reaction conditions, resulting in a
new synthetic method for valuable multi-substituted
perfluoroalkylated compounds.
During the last decade, some well-designed olefins have
been developed by many research groups for radical-induced
1,2-rearrangement. For example, the semipinacol-type
rearrangement[5] of allylic alcohols has been explored for the
preparation of diverse β-functionalized ketones (Figure 1a).[6]
Furthermore,
the
1,2-metalate
rearrangement[7]
of
vinylboronate complexes has been uncovered by using
Et3B/air,[8] visible light[9] or nickel catalysts[10] (Figure 1b).
Inspired by these results, our group also developed a
photoredox olefinic 1,2-boryl-migration by radical addition to
build gem-bis(boryl)alkanes.[11] In addition, the Studer group
has recently disclosed a novel 1,2-boryl-migration using
allylboronic esters to access radical 1,3-difunctionalization
products (Figure 1c).[12] Herein, we first describe that a class of
We started the investigations by treatment of olefin 1a with
I-nC4F9 (2a) (Table 1). The rearrangement was found to be
facile with 1.0 mol% fac-[Ir(ppy)3] as the photocatalyst (PC),
2.0 equiv of DBU as the base, in the presence of an additive,
TMDEA (2.0 equiv) in TFE after 12 h at room temperature
under irradiation with blue LEDs, and the desired product 3aa
was produced in 78% yield (entry 1). Under these reaction
conditions, a byproduct 4aa derived from atom transfer radical
addition (ATRA)[17] was formed in trace amounts. Replacing
the PC with [Ru(bpy)3]Cl2 or [Ir(ppy)2(dtbby)]PF6 afforded a
mixture of 3aa and 4aa (entries 2-3). Significantly, DBU and
[]
Z. Li, Assoc. Prof. Dr. M. Wang, and Prof. Dr. Z. Shi
State Key Laboratory of Coordination Chemistry, Chemistry
and Biomedicine Innovation Center (ChemBIC), School of
Chemistry and Chemical Engineering, Nanjing University,
Nanjing 210093 (China)
E-mail: shiz@nju.edu.cn
Supporting information and the ORCID identification
number(s) for the author(s) for this article can be found under
http://www.angewandte.org.
1
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10.1002/anie.202010839
Angewandte Chemie International Edition
Table 1. Reaction development.[a]
Table 2. Substrate scope of alkyl halides.[a]
Yield of
Yield of
Entry
Variation from the standard conditions
3aa (%)[b] 4aa (%)[b]
1
2
None
78 (73)[c]
<10
44
23
34
44
<10
<10
0
Using [Ru(bpy)3]Cl2 as PC
Using [Ir(ppy)2(dtbby)]PF6 as PC
Without DBU
15
27
39
<10
33
25
41
55
28
8
3
4
5
Without TMEDA
6
Using NEt3 instead of DBU
Using quinuclidine instead of DBU
Using MeOH instead of TFE
Using HFIP instead of TFE
Using DCM instead of TFE
Without [fac-Ir(ppy)3]
In the dark
7
8
9
0
10
11
12
8
57
0
0
[a]Reaction conditions: 1 mol% PC, 1a (0.20 mmol), 2a (0.40
mmol), DBU (0.40 mmol), TMEDA (0.40 mmol) in TFE (1.0 mL),
blue LEDs, at room temperature under Ar for 12 h. [b]GC yield.
[a]Reaction conditions: 1.0 mol% fac-[Ir(ppy)3], 1a (0.20 mmol), 2
(0.40 mmol), 2.0 equiv of DBU, 2.0 equiv of TMEDA, in 1.0 mL
TFE irradiated by blue LEDs, at room temperature under Ar for 12
h; Isolated yield. [b] Irradiated by 40 W blue LED.
[c]Isolated yield after chromatography. DBU
=
1,8-
diazabicyclo[5.4.0]undec-7-ene;
tetramethylethylenediamine.
TMEDA
=
N,N,N,N′-
TMEDA could accelerate the rearrangement process (entries 4-
5). Other organic bases, such as NEt3 and quinuclidine,
exhibited much lower reactivity for this transformation (entries
6-7). The TFE was superior to other alcohol solvents, such as
MeOH and HFIP (entries 8-9). When the reaction was
conducted in non-protonic solvents, such as DCM, the desired
product 3aa could also generate, albeit with a much lower
conversion (entry 10). Finally, control experiments showed that
both the PC and visible light were required for the
rearrangement (entries 11-12). The ATRA product 4aa could
be formed in the absence of PC in accordance with a radical
chain propagation process.
inexpensive and abundant agent CF3I (2n) was submitted to the
reaction conditions with olefin 1a, the desired product 3an was
generated in 69% yield. Gratifyingly, a higher yield of 6 (75%) was
observed while the reaction was performed using a TMEDA·2CF3I
adduct 2n'.[19] Furthermore, difluoromethylation of olefin 1a with
difluoromethyl 2-pyridyl sulfone 2o (Hu’s reagent)[20a] was also
facile to provide the rearrangement product 3ao in 56% yield.
Efforts to realize the monofluoromethylation of olefin proved
challenging, and the use of fluorosulfoximine reagent 2p[20b] only
showed low reactivity, potentially owing to the lack of radical
stabilizing groups.
With the optimized reaction conditions in hand, we first
performed a series of experiments to examine the scope of the
alkyl halides in this rearrangement reaction (Table 2). These
mild redox conditions were compatible with perfluoroalkyl
n
n
iodides bearing longer chains, such as C6F13I (2b) and C8F17I
2c). Difluoromethylating alkyl bromides 2d were also
(
-e
suitable substrates, and a monofluoromethylating substrate 2f
provides the corresponding product 3af with poor
diastereoselectivity. The generality of this reaction was further
proved by successful expansion to 1,1,1-trifluoro-2-iodoethane
(
2g) and analogs 2h-2i with longer perfluorinated chains.
Furthermore, tertiary aliphatic perfluoroalkyl iodides 2j-2k
could also be employed as radical precursors. Notably, the
reaction is not limited to the fluoro-containing substrates. Other
alkyl halides, such as ethyl 2-iodoacetate (2l), and 2-
iodoacetonitrile (2m), could also be used for the reaction,
Scheme 1. Fluoromethylation/1,2-aryl migration of alkene 1a.
affording desired products 2al-2am in good yields.
Given the important function of the fluoromethyl groups,[18]
we further anticipated that the 1,2-aryl migration would be
triggered by fluoromethylation (Scheme 1). When an
A
broad range of olefins can participate in this
rearrangement reaction with perfluoroalkyl iodide 2a as well
2
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10.1002/anie.202010839
Angewandte Chemie International Edition
(Table 3). Aryl motif bearing electron-donating and electron-
deficient substituents including OMe (1b), phenyl (1c), F (1d),
Br (1e) and CN (1f) groups at the para position facilitated
selectively be reduced to diol 5 (89%) or undergo decarboxylation to
ester 6 (81%) in good yields. Products bearing new all-carbon
quaternary centers could be generated from Michael addition (7),
nucleophilic substitution (8-9) and Aldol reaction (10) in 73-84%
yields. Finally, bromination of product 3an with NBS in the
presence of a base produced compound 11 in a modest yield.
facile migration, leading to products 3ba-3fa in 54-89% yields.
Substituents, such as CF3 (1g), COOEt (1h) and Cl (1i) in the
meta position of the aryl substituents were also compatible.
Product 3ja resulted from the migration of a naphthyl group
was isolated in moderate yield. Moreover, heteroaryl substrate
1k was submitted to the system and was found to give
rearrangement product 3ka in 80% yield. Pleasingly, this
strategy allowing for the rearrangement of olefins contains
diverse EWGs. The analogue 1l with two COOMe substituents
was readily transformed into 3la in a modest yield. The olefin
1m bearing one cyano and one ester group was also compatible.
However, reaction of substrate 1n possessing a bulky barbituric
acid motif with perfluoroalkyl iodide 2a provided ATRA
product 4na as a major product with trace amounts of the
desired product 3na (<10%). Notably, in the case of using Hu’s
reagent 2o with olefin 1n, the absence of I atom in substrate
resulted in a much higher conversion for the rearrangement
product, leading to the compound 3no in 51% yield. In addition,
the rearrangement of ethyl 2-ethyl-2-phenylbut-3-enoate (1o
)
containing only one EWG became very sluggish, in which the
ATRA compound 4oa was detected as a major product as well
(not shown in the Table).
Scheme 2. Follow-up transformations of compound 3an.
Some experiments were also performed to gain insight into
the potential mechanism of this rearrangement (Scheme 3).
Treatment of byproduct 4aa in the reaction did not form
product 3aa, excluding 4aa as the possible intermediate in this
reaction (Scheme 3a). As reported by Sodeoka’s results,[21] the
reaction of compounds 12-13 with longer alkenyl chains
formed cyclized products 14 and 15, and 1,n-aryl migration
products were not detected (Scheme 3b). When the reaction of
olefin 1a and alkyl halide 2d was conducted with d1-MeOH as
Table 3. Substrate scope of olefins.[a]
the solvent, D labeling was nearly fully incorporated into 3aa
.
Further detected by 13C NMR, the reaction mixture generated
two signals at 90.4 and 54.8 ppm, consistent with the formation
of d1-methoxymethanol (16) in this reaction.[22] Moreover,
treatment of compound 3aa in d1-MeOH did not form
deuterium product D-3aa (Scheme 3c). These results illustrate
[a]Reaction conditions: 1.0 mol% fac-[Ir(ppy)3], 1 (0.20 mmol), 2a
(0.40 mmol), 2.0 equiv of DBU, 2.0 equiv of TMEDA, in 1.0 mL
TFE irradiated by blue LEDs, at room temperature under Ar for 12
h; Isolated yield. [b]2o (0.40 mmol), without DBU, 4.0 equiv of
TMEDA, 24 h.
Because the rearrangement products contain two EWGs, we next
carried out some downstream transformations to demonstrate the
versatility of the current method (Scheme 2). The
trifluoromethylation reaction can be scalable to a 2.0 mmol scale to
afford compound 3an in 58% yield. This compound could
Scheme 3. Mechanistic experiments.
3
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10.1002/anie.202010839
Angewandte Chemie International Edition
that the H/D exchange process occurs during the reaction, and perfluoroalkylated organic compounds by visible-light
the alcohol solvent acts as a donor of the hydrogen atom for the photoredox catalysis. This strategy uses a series of vinyl-
products. Furthermore, “light/dark” experiments further substituted all-carbon quaternary centers to access cascade
confirmed that visible light was a necessary component of the
reaction. In addition, quantum yield measurements of the
radical addition, rearrangement, and reduction processes,
enabling one C-C bond cleavage along with one C-H and two
reaction between olefin 1a with I-nC4F9 (2a) yielded a value of C-C bond formations simultaneously. Further studies
Φ = 1.8 (see Supporting Information).[23] This result indicates
expanding upon the scope of this rearrangement as well as
that productive short-lived radical chain propagation processes further mechanistic investigations are currently underway.
perform alongside the main photoredox cycle.[24]
Based upon the above results and the previous reports, a
Acknowledgments
possible mechanism has been suggested in Figure 2.
Photoexcitation of the IrIII complex with visible light affords a
We wish to thank the National Natural Science Foundation of China
redox-active excited state *IrIII that undergoes single electron
(grant 21672097, 21972064 and 21901111), the National Natural
transfer (SET) with alkyl halides
and an alkyl radical
. The formed IrIV complex undergoes SET
with tertiary amines to recover the IrIII species and generate an
amine radical cation A [25]
Then, species can engage in
hydrogen atom transfer with the TFE solvent, delivering an
aminium species and carbon-centered radical . Further β-H
2
to produce an IrIV species
Science Foundation of Jiangsu Province (Grant BK20170632), the
Excellent Youth Foundation of Jiangsu Scientific Committee (Grant
BK20180007), and the “Innovation & Entrepreneurship Talents
Plan” of Jiangsu Province for their financial support.
I
.
A
B
C
Rearrangement ·fluorine·photochemistry ·radicals ·olefins
elimination delivers CF3CHO and a hydrogen atom radical. We
observed the formation of trifluoroethoxy hemiacetal 17 by
NMR from the reaction mixture, which was assumed to be
formed from CF3CHO and TFE.[26] Similarly, the use of d1-
MeOH as the solvent generates the deuterium product D-3aa
and HCHO, which can further react with d1-MeOH resulting in
compound 20 according to the experimental results. In addition,
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I
undergoes addition to olefin
1, providing
an alkyl radical II
.
Sequential 1,2-aryl migration via
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product
3.
2
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Entry for the Table of Contents (Please choose one layout)
Layout 2:
Rearrangement
Zexian Li, Minyan Wang, and Zhuangzhi
Shi*___ Page – Page
Radical Addition Enables 1,2-Aryl
Migration from Vinyl-Substituted All-
Carbon Quaternary Center
Lighting up: A photocatalytic system was developed for perfluoroalkylation of vinyl-
substituted all-carbon quaternary centers using perfluoroalkyl halides with
concomitant 1,2-aryl migration. This strategy possesses good functional group
compatibility and can serve as a powerful synthetic tool for construction of valuable
perfluoroalkylated compounds that would be difficult to prepare by other methods.
6
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