Alkylamination of Styrenes with Alkyl N-Hydroxyphthalimide Esters and Amines by B(C6H5)3-Facilitated Photoredox Catalysis

Article abstract of DOI:10.1021/acs.orglett.8b02670

A new, three-component 1,2-alkylamination of styrenes with alkyl N-hydroxyphthalimide (NHP) esters and amines by Lewis acid and visible-light photoredox cooperative catalysis is described. This reaction employs alkyl NHP esters as general alkylation reagents to accomplish the 1,2-alkylamination of alkenes in high efficiency and with excellent functional groups tolerance, significantly enhancing the synthetic potential of 1,2-alkylaminations of alkenes for accessing complex functionalized amines.

Full text of DOI:10.1021/acs.orglett.8b02670

Letter
pubs.acs.org/OrgLett
Cite This: Org. Lett. XXXX, XXX, XXX−XXX
Alkylamination of Styrenes with Alkyl N‑Hydroxyphthalimide Esters
and Amines by B(C6H5)3‑Facilitated Photoredox Catalysis
Xuan-Hui Ouyang,† Yang Li,† Ren-Jie Song,*,† and Jin-Heng Li*,†,‡
†Key Laboratory of Jiangxi Province for Persistent Pollutants Control and Resources Recycle, Nanchang Hangkong University,
Nanchang 330063, China
‡State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, China
S
* Supporting Information
ABSTRACT: A new, three-component 1,2-alkylamination of
styrenes with alkyl N-hydroxyphthalimide (NHP) esters and
amines by Lewis acid and visible-light photoredox cooperative
catalysis is described. This reaction employs alkyl NHP esters
as general alkylation reagents to accomplish the 1,2-
alkylamination of alkenes in high efficiency and with excellent
functional groups tolerance, significantly enhancing the synthetic potential of 1,2-alkylaminations of alkenes for accessing
complex functionalized amines.
mines are an important class of common compounds that
possess unique bioactivities and chemical properties and,
amino esters and pyrrolidin-2-ones; however, the reactions are
limited to α-bromoalkyl esters. Thus, new and efficient
strategies for intermolecular alkene 1,2-alkylamination, espe-
cially including utilizations of new alkylation reagents, are still
highly appealing.
A
thus, serve not only as a key structural motif in numerous
natural products and pharmaceuticals but also as important
synthetic building blocks in synthesis. Among the efficient
methods that have been established for constructing diversely
functionalized amines,1 the carboamination of alkenes has
proven to be a particularly powerful technology for
incorporating amine elements across CC bonds leading to
valuable amino-functionalized molecules.2,3 However, exam-
ples of the alkylamination of alkenes in which an amine and an
alkyl group are simultaneously introduced across the CC
bond of an alkene are rare (Scheme 1a).3 Recently, we
Alkyl NHP esters have become general and readily available
alkylation reagents for decarboxylation reactions under visible-
light photoredox catalysis or metal catalysis.4−7 However, the
vast majority of successful approaches focus on two-
component decarboxylative alkylation processes, most likely
due to the high instability of the alkyl radicals. Typical
approaches include transformations of alkyl NHP esters with
alkenes, and most of these reactions are limited to a two-
component decarboxylative Heck-type alkylation reaction and
hydroalkylation process.5 In 2017, the Glorius group6a
reported a new multicomponent oxyalkylation of styrenes
with alkyl NHP esters and H2O or alcohols, which was
achieved by activating N-(acyloxy)phthalimides toward photo-
induced electron transfer through hydrogen bonding. Sub-
sequently, the Glorius group6b and the Ye group6c
independently employed DMSO as the oxygen source and
oxidant to realize the oxoalkylation of styrenes with alkyl NHP
esters under photocatalysis. Very recently, a photoredox and
copper-catalyzed asymmetric cyanoalkylation using alkyl NHP
esters as alkylation reagents and TMSCN as the CN source
was developed.6g On the basis of these results, we envisioned
that the combination of a Lewis acid and a photocatalyst might
allow the reactivity of the alkyl radicals to be controlled,
providing selective for addition across the CC bond and
suppressing the competitive direct coupling with strong
nucleophiles and β-H elimination. Herein, we report a novel
three-component 1,2-alkylamination of alkenes with alkyl NHP
Scheme 1. Intermolecular Alkene 1,2-Alkylamination
reported a new 1,2-alkylamination of alkenes to access γ-amino
alkyl nitriles by using alkyl nitriles as the alkyl sources in the
presence of an amines, and the reaction is catalyzed by Lewis
acidic iron and Ag2CO3 is used as the oxidant.3a Bao and co-
workers3b have employed aliphatic diacyl peroxides as general
alkylating and oxidizing agents and nitriles as nitrogen sources
to extend an Fe-catalyzed alkene alkylamination methodology.
The Hull group3c and our group3d,e independently developed a
Cu-catalyzed oxidative intermolecular 1,2-alkylamination of
alkenes with alkyl bromides and amines for the synthesis of γ-
Received: August 21, 2018
© XXXX American Chemical Society
A
DOI: 10.1021/acs.orglett.8b02670
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
a
esters and amines enabled by the synergistic combination of
photoredox and Lewis acid catalysts to produce valuable alkyl-
functionalized amines (Scheme 1b). Employing the combina-
tion of Ru(bpy)3Cl2, B(C6H5)3, and blue light allows the
formation of two new chemical bonds, namely, a C(sp3)−
C(sp3) bond and a C(sp3)−N bond, in good efficiency
through a decarboxylative generation of an alkyl radicals,
addition across the alkenes, and nucleophilic amination
cascade process.
Scheme 2. Variations of the Alkyl NHP Esters (2)
Our study of the 1,2-aminoalkylation of alkenes began with
exposure of the three reaction partners, 4-methoxystyrene 1a,
cyclohexyl NHP ester 2a, and 2,3-dimethylaniline, to the
visible-light cooperative catalysis system (Table 1). Employing
a
Table 1. Screening of Optimal Reaction Conditions
a
Reaction conditions: 1a (0.2 mmol), 2 (1.5 equiv), 3a (1.5 equiv),
Ru(bpy)3Cl2 (1 mol %), B(C6F5)3 (10 mol %), DMSO (1 mL), 5 W
LED blue light, argon, room temperature, and 24 h.
entry
photocatalyst
Ir(ppy)3
Ir(ppy)3
additive
solvent
yield (%)
1
2
3
4
5
6
DMSO
NMP
31
7
9
Ir(ppy)3
MeCN
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
[Ir(dtbbpy)(ppy)2](PF6)2
Ru(bpy)3Cl2
Eosin Y
Ru(bpy)3Cl2
Ru(bpy)3Cl2
Ru(bpy)3Cl2
Ru(bpy)3Cl2
Ru(bpy)3Cl2
Ru(bpy)3Cl2
34
38
5
24
36
32
31
52
50
substrates and provided 4aba−ama in moderate to good
yields, and 3° alkyl groups were more reactive than 1° and 2°
alkyl groups. 1-Methylcyclohexyl- or adamantyl-possessing
NHP esters 2b,c and 4aba−aca were delivered in high yields,
but 3° bridge ring-containing NHP ester 2d furnished 4ada in
moderate yield, probably due to the electron-withdrawing ester
group. The 2° alkyl groups, including cycloheptyl (2e),
cyclopentyl (2f), tetrahydrofuran-2-yl (2g), and pent-3-yl
(2i), led to 4aea−4aga and 4aia in moderate yields. Two
other 3° alkyl groups, 1-phenylcyclopropyl (2h) and tert-butyl
(2j), were well accommodated to assemble 4aha and 4aja.
Using 1° alkyl groups, such as n-hexyl (2k), n-undecyl (2l),
and 4-ethoxy-4-oxobutyl (2m), enabled the formation of
4aka−ama. For example, 4-ethoxy-4-oxobutyl NHP ester 2m
was smoothly transformed into 4ama, showing that an ester
group was tolerated. Unfortunately, phenyl NHP ester 2n was
unsuitable for the reaction (4ana).
This three-component 1,2-aminoalkylation protocol was
general for styrenes 1a−m and amines 3b−n (Scheme 3). In
the presence of adamantyl NHP ester 2c, Ru(bpy)3Cl2, and
B(C6F5)3 under blue light, a variety of other primary
arylamines 3b−i were suitable substrates for accessing 4acb−
aci in moderate yields, and a number of substituents, including
MeO, Cl, I, CN, and phenylethynyl, on the aryl ring were
tolerated. Both aniline 3b and naphthalen-1-amine 3i were
successfully introduced across the alkene 1a (4acb and 4aci).
Using valuable secondary amines, such as N-methylaniline 3j,
indoline 3k, 1,2,3,4-tetrahydroquinoline 3l, and 3,4-dihydro-
2H-benzo-[b][1,4]oxazine 3m, efficiently enabled the for-
mation of the desired products 4acj−acm. However,
piperidine, an aliphatic amine, had no reactivity (4acn). We
found that the optimal conditions were compatible with a wide
range of terminal arylalkenes 1b, 1d−j (4bcb, 4dcb−jcb) and
an internal alkene 1l (4lcb) but did not work with the electron-
deficient p-CN-substituted arylalkene 1c (4ccb), alkylalkene
1k (4kcb), and indene 1m (4mcb). In the case of styrenes 1b
and 1d comprising a p-Me or an o-MeO group, the reaction
proceeded smoothly to furnish 4bcb and 4dcb in moderate
b
7
8
9
BF3·Et2O
Fe(OTf)3
NiBr2
B(C6F5)3
B(C6F5)3
10
11
12
c
a
Reaction conditions: 1a (0.2 mmol), 2a (1.5 equiv), 3a (1.5 equiv),
photocatalyst (1 mol %), additive (10 mol %), solvent (1 mL), 5 W
LED blue light, argon, room temperature, and 24 h. Some byproducts,
including (E)-1-(2-cyclohexylvinyl)-4- methoxybenzene 5aa and N-
cyclohexyl-2,3-dimethylaniline 6aa, were observed as determined by
b
c
GC−MS analysis. 36 W compact fluorescent light. At 40 °C.
Ir(ppy)3 photocatalyst and blue light in DMSO, the desired
product 4aaa was formed in 31% yield (entry 1). Two other
solvents, 1-methyl-pyrrolidin-2-one (NMP; entry 2) and
MeCN (entry 3), showed lower reactivity than DMSO. A
survey of photocatalysts proved Ru(bpy)3Cl2 to be the optimal
choice, as the other three photocatalysts (entries 4−6),
namely, Ir(ppy)3, [Ir(dtbbpy)(ppy)2](PF6)2, and eosin Y, all
gave lower yields than Ru(bpy)3Cl2. A compact fluorescent
light also accommodated the reaction, albeit in diminished
yield (entry 7). Gratifyingly, Lewis acids, such as BF3·Et2O,
Fe(OTf)3, NiBr2, and B(C6F5)3, were found to affect the
reaction (entries 8−11). While the first three Lewis acids had a
deleterious effect (entries 8−10), the last B(C6F5)3 Lewis acids
enhanced the yield of 4aaa to 52% yield (entry 11). A higher
temperature (40 °C) was screened with no improvement on
the yield (entry 12).
With the optimal reaction conditions in hand, we explored
the scope of this three-component 1,2-aminoalkylation
protocol with respect to alkyl NHP esters 2b−n (Scheme 2).
In the presence of alkene 1a and amine 3a, Ru(bpy)3Cl2,
B(C6F5)3, and blue light, a variety of alkyl NHP esters 2b−m
comprising 1°, 2°, and 3° alkyl groups were all suitable
B
DOI: 10.1021/acs.orglett.8b02670
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
a
The plausible mechanism for this three-component alkene
1,2-aminoalkylation protocol is outlined in Scheme 4.2−5,7
With the aid of visible-light photoredox catalysis and B(C6F5)3,
cyclohexyl NHP ester 2a is decomposed and generates the
cyclohexyl radical A, CO2, and phthalimide anion. Addition of
the cyclohexyl radical A across the CC bond of arylalkene 1
selectively occurs to form alkyl radical B, which sequentially
undergoes single electron oxidation by the [Ru(bpy)3]3+
species to afford the alkyl cation intermediate C. Finally, the
reaction of the intermediate C with nucleophilic amine 3a
delivers the desired product 4. Meanwhile, intermediate C
resulted in the formation of byproduct 5 via β-H elimination.
The quantum yield (Φx = 0.014) rules out a chain
mechanism.8
Scheme 3. Variations of the Alkenes (1) and Amines (3)
During the processes, both intermediates B and C require
conjugation of the Lewis acid to make them sufficiently stable;
thus, only styrenes display high reactivity. B(C6F5)3 might
serve as a Lewis acid to activate the N-(acyloxy)phthalimides,
intermediate A, and intermediate B.
In summary, we have developed a novel, three-component
1,2-aminoalkylation of styrenes by Lewis acid and visible-light
photoredox cooperative catalysis in which alkyl N-hydroxyph-
thalimide esters are employed as the alkylation reagents and
are used amines as the nucleophilic termination reagents. This
reaction provides a practical route to access various function-
alized secondary and tertiary amines through the formation of
two new chemical bonds, a C(sp3)−C(sp3) bond and a
C(sp3)−N bond. Moreover, the reaction features high
selectivity and broad substrate scope with regard to a wide
range of styrenes, alkylation reagents, and amines; thus, this
reaction represents an indisputable advance in the 1,2-
aminoalkylation of alkene field for the construction of valuable
amine architectures.
a
Reaction conditions: 1 (0.2 mmol), 2c (1.5 equiv), 3 (1.5 equiv),
Ru(bpy)3Cl2 (1 mol %), B(C6F5)3 (10 mol %), DMSO (1 mL), 5 W
LED blue light, argon, room temperature, and 24 h.
yields. Both styrene 1e and 1-vinylnaphthalene 1f were suitable
substrates, but the yields of the corresponding products
(4ecb−fcb) were lower. Disubstituted styrenes 1h,i were
found to be highly reactive, giving 4hcb−icb in high yields. It
was noted that 2-methyl-3-vinylthiophene 1j provided sulfur-
containing heteroaryl-functionalized product 4jcb. This
protocol was applicable to internal alkene 1l, which gave
4lcb in 43% yield. However, it could not run with indene 1l
(4lcb). Surprisingly, 1,1-diphenylethene 1n only afforded the
Heck-type product 5n (eq 1; Scheme 4).
To gain insight into the mechanism, control experiments of
alkene 1a with NHP ester 2a and amine 3a were conducted in
the presence of a radical inhibitor, such as TEMPO,
hydroquinone, and BHT (eq 2; Scheme 4). The reaction
was completely suppressed, which supports a radical process.
ASSOCIATED CONTENT
■
S
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.or-
glett.8b02670.
Descriptions of experimental procedures for compounds,
and analytical characterization (PDF)
Scheme 4. Control Experiments and Possible Mechanism
AUTHOR INFORMATION
■
Corresponding Authors
*E-mail: srj0731@hnu.edu.cn.
*E-mail: jhli@hnu.edu.cn.
ORCID
Ren-Jie Song: 0000-0001-8708-7433
Jin-Heng Li: 0000-0001-7215-7152
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We thank the National Natural Science Foundation of China
(Nos. 21625203 and 21472039) and the Jiangxi Province
Science and Technology Project (Nos. 20171ACB20015 and
20165BCB18007) for financial support.
C
DOI: 10.1021/acs.orglett.8b02670
Org. Lett. XXXX, XXX, XXX−XXX

Organic Letters
Letter
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Org. Lett. XXXX, XXX, XXX−XXX