Construction of Boronated γ-Lactams via Palladium-Catalyzed Intramolecular Boryldifluoroalkylation of Alkenes

Article abstract of DOI:10.1002/adsc.202000786

An approach for the preparation of boronated γ-lactams via palladium-catalyzed boryldifluoroalkylation of alkenes with α-bromodifluoroacetamides was developed. This method exhibits good functional group tolerance. Various boronated products were obtained in moderate to good yields for 1 h. Mechanistic studies indicated that this reaction may involve an intramolecular radical cascade cyclization process. (Figure presented.).

Full text of DOI:10.1002/adsc.202000786

Title: Construction of Boronated γ-Lactams via Palladium-Catalyzed
Intramolecular Boryldifluoroalkylation of Alkenes
Authors: Wu-Jie Lin, Yu-Zhao Wang, Jian-Yu Zou, Yi-Chuan Zhao, Jin-
Lin Wang, and Xue-yuan Liu
This manuscript has been accepted after peer review and appears as an
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.202000786
Link to VoR: https://doi.org/10.1002/adsc.202000786

10.1002/adsc.202000786
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201
Construction of Boronated γ-Lactams via Palladium-Catalyzed
Intramolecular Boryldifluoroalkylation of Alkenes
Wu-Jie Lin,a Yu-Zhao Wang,a Jian-Yu Zou,a Yi-Chuan Zhao,a Jin-Lin Wang,a and Xue-
Yuan Liua,*
aState Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou
University, Lanzhou, 730000, People’s Republic of China
E-mail: liuxuey@lzu.edu.cn
Received:
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.
ubiquitous existence of fluorine skeletons in natural
lactams via palladium-catalyzed boryldifluoroalkylation of products, pharmaceuticals and agrochemicals.[7]
Abstract. An approach for the preparation of boronated γ-
alkenes with α-bromodifluoroacetamides was developed.
This method exhibits good functional group tolerance.
Various boronated products were obtained in moderate to
good yields for 1h. Mechanistic studies indicated that this
reaction may involve an intramolecular radical cascade
cyclization process.
Generally, the methods to introduce CF2 group mainly
focus on transition-metal-catalyzed cross-couplings[8]
and free radical process.[9] Several elegant examples
in
transition-metal-catalyzed
difluoroalkylation
reactions have been developed in recent years,
offering efficient routes to construct the fluorinated
compounds. For example, Zhang and co-workers
developed
a
palladium-catalyzed
Heck-type
Keywords: alkenes; boronation; difluoroalkylation;
difunctionalization; palladium-catalyzed
fluoroalkylation of alkenes with fluoroalkyl halides,
which involves a radical pathway.[9i] Our group also
reported a palladium-catalyzed regioselective radical
difluoroalkylation and carbonylation of alkynes.[10]
A
visible-light-mediated tandem radical difluoroalkylat-
ion of unactivated alkenes was developed by Zhu
group.[11] Despite these promising advances,[12] new
and efficient methods for incorporating the
difluoromethylene group (CF2) into organic
compounds is still highly desirable.
Organoboron compounds are useful building
blocks in organic synthesis, and the carbon-boron
bond can be readily transformed into various
functional groups.[1] Considerable efforts have been
devoted to the construction of boron-containing
molecules.[2] Among various approaches, the
difunctionalization of alkenes is one of the most
efficient methods,[3] leading to rapidly increase in
molecular complexity via a single synthetic operation.
In this context, the boryldifluoroalkylation of alkenes
has made remarkable achievement owing to the
ubiquity of CF2 group.[4], [5] For examples, in 2018,
Studer et al. reported a transition metal-free radical
carboboration reaction of unactivated alkenes
(Scheme 1a).[5] This method allows the conversion of
various unactivated alkenes into 1,2-addition products
by light-mediated C-I bond homolysis. Subsequently,
Zhu and Zhang reported the novel palladium-
catalyzed carboboration reaction of alkynes with
fluoroalkyl halides, independently (Scheme 1b).[6]
This approach shows high regio- and stereoselectivity
and broad substrate scope, trans-addition product.
However, to the best of our knowledge,
intramolecular boryldifluoroalkylation of alkenes is
not reported.
γ-Lactams are common structural motifs found in
natural products and pesticides. The CF2-containing
Scheme1. boryldifluoroalkylation of alkenes or alkynes
γ-lactams are of particularly attractive due to their
unique pharmacological properties.[13] Consequently,
new methods to construct fluorinated γ-lactams are
desirable.[14] As part of our ongoing interest in CF2
Difluoroalkylation reactions have attracted
chemists’ persistent attention because of the
1
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10.1002/adsc.202000786
Advanced Synthesis & Catalysis
chemistry[15] and C-B bond formation, here we report ly, variation of the solvents was then conducted
a palladium-catalyzed intramolecular boryldifluoroal- (entries 10-12), which showed acetonitrile (CH3CN)
kylation of alkenes with B2pin2 (Scheme 1c). The to be the most efficient (entry 12). When the reaction
reaction involves tandem radical cyclization, and it temperature was raised to 80 oC and the amount of
affords a series of useful 4-boronate ester substituted
Scheme 2. Scope of the Bromodifluoroacetamidesa
difluoro-γ-lactams.
Initially, we used N-allyl-2-bromo-2,2-difluoro-N-
phenylacetamide 1a and B2pin2 as model substrates to
investigate the feasibility of this reaction (Table 1).
When the reaction proceeded with CuI/2, 2'-bpy (10
mol%) and LiOtBu (1.5 equiv.) in DMF at 60 °C, the
desired product 3a was obtained in 14% yield (entry
1). The use of other representative Cu catalysts,
including CuBr and Cu(CH3CN)4PF6 did not result in
any improvement in yields (entries 1-3). Then we
tested commonly used Pd catalysts to improve yields.
A 42% yield of 3a was obtained when Pd(PPh3)4 was
used (entry 4). Then, we continued to examine other
reagents to improve yields, the results demonstrated
that Cs2CO3 was the optimized base (entries 5-9) and
obtained the target product in 46% yield. Subsequent-
Table 1. Optimization of reaction conditionsa.
Entr
y
Yields
b (%)
14
Catalyst/L
Base
Solvent
1c
CuI/2, 2'-bpy
CuBr/2, 2'-bpy
Cu(CH3CN)4PF6/2,
2'-bpy
LiOtBu
LiOtBu
DMF
DMF
2c
9
3c
LiOtBu
DMF
13
4c
5c
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
no
LiOtBu
K2CO3
Na2CO3
K3PO4
Cs2CO3
Et3N
DMF
DMF
DMF
DMF
DMF
DMF
42
37
20
43
46
trace
48
46
51
65
72
61
59
71
75
0
6c
7c
8c
9c
10c
11c
12c
13d, e
14d
15d, f
16d, g
17e
18
Cs2CO3 toluene
Cs2CO3 THF
Cs2CO3 CH3CN
Cs2CO3 CH3CN
Cs2CO3 CH3CN
Cs2CO3 CH3CN
Cs2CO3 CH3CN
Cs2CO3 CH3CN
Cs2CO3 CH3CN
Cs2CO3 CH3CN
19
20
Pd(PPh3)4
no
CH3CN
0
aUnless otherwise noted, all reactions were performed with
1a (0.1 mmol), catalyst (10 mol%), B2pin2 (2.0 equiv) and
base (2.0 equiv) in solvent (1.0 mL) at 80 °C under an
aReactions were carried out with 1 (0.1 mmol), B2pin2 (2.0
equiv), Pd(PPh3)4 (10 mol%), and Cs2CO3 (2.0 equiv) in
CH3CN (1.0 mL) under Ar atmosphere at 80 °C for 1 h.
bIsolated yields. cBromodifluoroacetamide was replaced by
b
c
argon atmosphere for 1 h. Isolated yields. Reaction was
performed with base (1.5 equiv), B2pin2 (1.5 equiv) at 60
oC for 11 h. B2pin2 (1.5 equiv) was used. Reaction was
d
e
f
performed for 11 h. Reaction was performed for 2 h.
d
gReaction was performed for 8 h. 2, 2'-bpy = 2, 2'-
bipyridine, 1, 10-Phen = 1, 10-phenanthroline.
chlorodifluoroacetamide. NMR yield with methoxybenzi-
ne as internal standard.
2
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10.1002/adsc.202000786
Advanced Synthesis & Catalysis
base was increased to 2.0 equivalent, yield gave rise Scheme 5. Mechanistic Study
to 65% (entry 13). Notably, shortening reaction time
could improve reaction efficiency (entries 14-16).
Finally, when the reaction was performed with B2pin2
(2.0 equiv) under Pd(PPh3)4 (10 mol%) as catalyst and
o
Cs2CO3 (2.0 equiv) as base at 80 C for 1 h, resulted
in the best result, affording 3a in 75% yield (entry 18).
Control experiments indicated that no desired product
was observed in the absence of catalyst or base
(entries 19 and 20).
hydrolysate 3y’ instead. The structure of 3p was
confirmed by X-ray crystallographic analysis (CCDC
No. 2011001).[16]
To our delight, this reaction could scaled up to
large quantities. When 3.4 mmol of 1a and 6.8
mmol of 2 were performed under standard
conditions, a 55% yield of the desired product 3a was
isolated (Scheme 3).
To showcase the synthetic ultility of this
methodology, we studied the derivation of the
products (Scheme 4). By treating the product with
NaBO3·4H2O, difluoroalkylated alcohols were
obtained in moderate yield. Furthermore, by treating
3a with PhBr in the presence of a palladium catalyst,
arylated product 5a was obtained in 50% yield.
In order to gain the mechanism of this
transformation, several control experiments were
conducted (Scheme 5). When radical inhibitor (2.0
equiv), TEMPO or BHT, added, the reaction was
completely inhibited. These results indicated that a
radical pathway might be involved in this process.
On the basis of these experiments and previous
reports,[6] a plausible reaction mechanism is shown in
Scheme 6. Initially, single electron transfer (SET)
between Pd(0) and bromodifluoroacetamide 1a
generates a radical intermediate A and Pd(I)X species.
Next, an intramolecular cyclization through addition
With the optimized reaction conditions established,
we studied the substrate scope of this reaction.
Various bromodifluoroacetamides were investigated
and the results are illustrated in Scheme 2. The
bromodifluoroacetamides, bearing electron-donating
and electron-withdrawing groups, all worked well in
this protocol, affording the corresponding 4-boronated
difluoro-γ-lactams in moderate yields (3b-3o).
Substrates with halogen substituents also worked well,
offering an entry for further transformation (3j-3m).
Sterically hindered substrates, 1d and 1u, failed to
produce the desired product. Bromodifluoroacetamide
-s with multiple substituents were tolerated,
furnishing the desired products in moderate yields
(3q-3s). The substrate
bearing heterocyclic
substituent was also applicable to this transformation
(3w). The N-homoallyl amide 1y also participated in
this transformation, generating the 6-exo-trig cyclic
product in a moderate yield. The Product 3y was
difficult to separate, so we obtained the corresponding
Scheme 3. Scale-up Reaction
Scheme 6. Proposed Mechanism
Scheme 4. Derivatization of the Product
3
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10.1002/adsc.202000786
Advanced Synthesis & Catalysis
of the fluoroalkyl radical on the double bond affords
radical intermediate B. Subsequently, the reaction of
intermediate B with Pd(I)X species forms the Pd(II)
intermediate C, which undergoes transmetalation with
B2pin2 to deliver complex D. Finally, the reductive
elimination of intermediate D generates the desired
product 3a. This process also regenerates Pd(0),
which enters into the next catalytic circle.
In summary, we have demonstrated a palladium-
catalyzed reaction for the construction of 4-boronate
ester substituted difluoro-γ-lactams. This strategy is
easy to operate, and it provides a simple route to
produce 4-boronated difluoro-γ-lactams that are
difficult to access otherwise. The broad substrate
scope, short reaction time and potential product
derivatization make the boryldifluoroalkylation
reactions very attractive. Preliminary mechanistic
studies revealed that this reaction may involve an
intramolecular difluoroalkyl radical cyclization
process. Given that the unique merit of organoboron
species, we believe this method has potential
application on synthetic chemistry.
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Financial support from the National Natural Science Foundation
of China (21871115) is gratefully acknowledged.
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5
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10.1002/adsc.202000786
Advanced Synthesis & Catalysis
COMMUNICATION
Construction of Boronated γ-Lactams via
Palladium-Catalyzed
Intramolecular
Boryldi-
fluoroalkylation of Alkenes
Adv. Synth. Catal. Year, Volume, Page – Page
Wu-Jie Lin,a Yu-Zhao Wang,a Jian-Yu Zou,a Yi-
Chuan Zhao,a Jin-Lin Wang,a and Xue-Yuan Liua,*
6
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