Deaminative (Carbonylative) Alkyl-Heck-type Reactions Enabled by Photocatalytic C?N Bond Activation

Article abstract of DOI:10.1002/anie.201813689

The palladium-catalyzed Heck reaction is a well-known, Nobel Prize winning transformation for producing alkenes. Unlike the alkenyl and aryl variants of the Heck reaction, the alkyl-Heck reaction is still underdeveloped owing to the competitive side reactions of alkyl–palladium species. Herein, we describe the development of a deaminative alkyl-Heck-type reaction that proceeds through C?N bond activation by visible-light photoredox catalysis. A variety of aliphatic primary amines were found to be efficient starting materials for this new process, affording the corresponding alkene products in good yields under mild reaction conditions. Moreover, this strategy was successfully applied to deaminative carbonylative alkyl-Heck-type reactions.

Full text of DOI:10.1002/anie.201813689

A Journal of the Gesellschaft Deutscher Chemiker
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Accepted Article
Title: Deaminative (Carbonylative) Alkyl-Heck-type Reactions Enabled
by Photocatalytic C-N Bond Activation
Authors: Wen-Jing Xiao, Xuan Jiang, Mao-Mao Zhang, Wei Xiong, and
Liang-Qiu Lu
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201813689
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10.1002/anie.201813689
Angewandte Chemie International Edition
COMMUNICATION
Deaminative (Carbonylative) Alkyl-Heck-type Reactions Enabled
by Photocatalytic C-N Bond Activation
Xuan Jiang,[a] Mao-Mao Zhang,[a] Wei Xiong,[a] Liang-Qiu Lu,*,[a] and Wen-Jing Xiao*,[a,b]
Abstract: The Pd-catalyzed Heck reaction is a well-known, Nobel
Prize-awarded transformation for producing alkenes. Unlike the
state-of-the-art alkenyl- and aryl-Heck reaction, the alkyl-Heck
reaction is still underdeveloped due to the competitive side reactions
of alkyl-Pd species. In this work, a deaminative alkyl-Heck-type
reaction was developed through C-N bond activation by visible-light
photoredox catalysis. A variety of aliphatic primary amines together
with alkenes were determined to be efficient feedstock for this new
protocol, affording alkene products in good yields under mild
conditions. Moreover, this strategy can be successfully extended to
deaminative carbonylative alkyl-Heck-type reactions.
transformations.[10] In 2017, Watson reported a Ni-catalyzed
deaminative C-C coupling reaction of Katritzky salts with boronic
acids at room temperature.[11] Soon after, Glorius developed a
visible-light
photocatalytic
deaminative
alkylation
of
heteroarenes by using Katritzky salts.[12] Both of these mild-
condition transformations were built heavily on the single
electron reduction (SER) of Katritzky salts to reactive alkyl
radicals. Inspired by these advances and following our interest in
organic photochemical synthesis,[13] we envisioned that this
concept could be used for the deaminative alkyl-Heck-type
reaction and carbonylative alkyl-Heck-type reaction of
alkylamines through visible-light photoredox catalysis (PC).
Clearly, this study represents a complementary protocol to the
previously developed Heck reactions described above, featuring
mild reaction conditions and readily available starting materials.
The delivery of new protocols complementary to state-of-the-art
transformations is a central goal of modern chemical synthesis.
In 2010, the Heck reaction, which was pioneered by Heck and
Mizoroki in approximately 1970,[1] was awarded the Nobel Prize
in Chemistry together with other two Pd-catalyzed coupling
reactions because these reactions revolutionized organic
chemistry and related pharmaceutical and materials science
fields.[2] Despite the revolutionary advances of nearly half a
century and compared with the Heck reaction of unsaturated
halide (or triflate) substrates, alkyl-Heck reactions are still
underdeveloped due to the inherent instability of alkyl palladium
species (i.e., the preference for the competing β-hydrogen
elimination over the insertion reaction with alkene).[3] Until
recently, significant breakthroughs have been made in this field
by replacing traditional two-electron pathways with single-
electron-transfer (SET) processes.[4-7] In these studies, redox-
reactive substrates such as activated alkyl halides and
carboxylic acids have been commonly applied as efficient alkyl
radical sources in alkyl-Heck-type reactions.[5-7] Despite this
impressive achievement, efforts toward expanding the range of
alkyl radical sources are still important for the synthetic
community because new protocols would streamline alkene
synthesis and realizes novel functional group transformations.
Alkylamines are fundamental compounds that are widely
found in natural products and synthetic chemicals.[8] However,
their potential as effective carbon sources in organic synthesis is
still underexploited, possibly due to the high bond energy of the
sp3 C-N bonds.[9] In approximately 1980, Katritzky found that
converting primary alkylamines into pyridinium salts (namely,
Katritzky’s salts) can efficiently activate inert C-N bonds;
however, high temperatures are still required for further
Scheme 1. Reaction design: deaminative (carbonylative) Heck-type reactions.
We began this study by choosing a Katritzky salt 1a and 1,1-
diphenyl ethylene 2a as the model substrates, an iridium
complex [Ir]-1 as the photocatalyst and DABCO as the base
under irradiation by 2ｘ3 W blue LEDs in CH3CN (Table 1). To
our delight, the reaction proceeded very well under the initial
conditions, leading to the formation of product 3aa in 86% NMR
yield (entry 1).
A variation of photocatalysts, including
Ru(bpy)3Cl2•6H2O and other Ir-based photocatalysts, did not
provide improved yields (entries 2-4). The replacement of
DABCO with other bases resulted in worse yields (entries 5 and
6), while a lower DABCO concentration slightly improved the
reaction yield (entry 7, 93% yield). Control experiments implied
that both visible light and a photocatalyst are necessary for the
present transformation and that the absence of DABCO resulted
in a slightly lower yield (entries 8-10).
[a]
X. Jiang, M.-M. Zhang, W. Xiong, Prof. Dr. L.-Q. Lu, Prof. Dr. W.-J.
Xiao
Key Laboratory of Pesticide & Chemical Biology Ministry of
Education, College of Chemistry, Central China Normal University,
152 Luoyu Road, Wuhan, Hubei 430079, China
E-mail: luliangqiu@mail.ccnu.edu.cn; wxiao@mail.ccnu.edu.cn
Under the optimum reaction conditions, we observed a broad
scope of Katritzky salts that were prepared from primary
alkylamines. As highlighted in Table 2, both cyclic and acyclic
amine substrates were efficiently converted to alkenylation
products in good yields (3aa-3ia: 65-97% yields). In particular,
fluorine-containing carbocyclic and O- or N-heterocyclic
substrates also participated well in this transformation (3fa-3ia,
65%-93%). Other Katritzky salts prepared from functionalized
alkylamines, such as benzyl amine, α-amino acetonitrile and
amino acid esters, were tolerant of the photocatalysis system,
[b]
Prof. Dr. W.-J. Xiao
State Key Laboratory of Organometallic Chemistry, Shanghai
Institute of Organic Chemistry, Chinese Academy of Sciences,
Shanghai 200032, China
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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10.1002/anie.201813689
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COMMUNICATION
Table 1. Condition optimization for the deaminative Heck-type reaction.[a]
very well to generate the alkene product 3ma in 81% yield.
Furthermore, a commercially available dipeptide and an anti-
diabetic drug, Alogliptin,[14a] were chosen as two platform
molecules to demonstrate the potential of this deaminative
Heck-type reaction. Indeed, these two transformations produced
the deaminative alkenylation derivatives in moderate and high
yields, respectively (Table 2, 3na: 61% yield; 3oa: 92% yield).
Notably, the diversification of commercial drug molecules is well-
accepted to be a fruitful approach to pharmaceutical candidate
discovery.[14b]
Entry
Variation of initial reaction conditions
No variation
Yield[b]
86%
1
2
Replace [Ir]-1 with [Ru]
73%
3
Replace [Ir]-1 with [Ir]-2
83%
Subsequently, we continued to probe the scope of the alkene
partner under the optimum conditions. As summarized in Table
3, the electronic properties of the diarylalkenes were examined
in the deaminative alkyl-Heck-type reaction. Substrates with
weakly electron-withdrawing groups (F-, Cl-) or electron-
donating group (Me-) at the 4-position of the benzene ring
exhibited higher reaction efficiency than those with electron-rich
substrates (MeO-, Me2N-) and the 4-phenyl-substitued substrate.
This might be the result of higher reactivity of electro-deficient
diaryl alkenes to nucleophilic alkyl radicals.[6c,7c] Overall, all the
reactions proceeded well under the standard photocatalytic
conditions (4ib-4ig, 68% to 95% yields). Delightedly, this
success was extended to cyclic arylalkenes and cinnamylic acid,
delivering the corresponding products (4ih, 60% yields; 4ai, 66%
yields). Moreover, we found that α-aryl, α-heteroaryl silyl enol
ethers or amide-derived enamines could be used as effective
coupling partners, affording ketone products or a new enamine
in moderate to high yields (5ib-5id, 5ke, 5af: 40% to 93% yields).
4
Replace [Ir]-1 with [Ir]-3
77%
5
Replace DABCO with DIPEA
Replace DABCO with K2HPO4
Performed at 0.08 M
35%
6
72%
7
93% (91%)[c]
0%
8
Performed in dark at 0.08 M
Performed without [Ir]-1 at 0.08 M
Performed without DABCO at 0.08 M
9
3%
10
84%
[a] Initial reaction conditions: 1a (0.2 mmol), 2a (0.32 mmol), [Ir]-1 (2.5 mol%),
DABCO (0.2 mmol), in CH3CN (2.5 mL) at 40 °C under an argon atmosphere
and irradiation by 2x3 W blue LEDs. [b] Determined by 1H NMR analysis using
3,5-dimethyltoluene as the internal standard. [c] Isolated yield in parentheses.
DABCO: 1,4-diazabicyclo [2.2.2]octane; [Ir]-1: Ir(4-Fppy)2(bpy)PF6; [Ir]-2:
Ir(ppy)2(dtbbpy)PF6; [Ir]-3: Ir(2,4-dFppy)2(bpy)PF6; [Ru]: Ru(bpy)3Cl2•6H2O.
and the corresponding products were produced in moderate to
good yields (3ja-3ma: 34%-87% yields). To demonstrate the
utility of this methodology, a gram-scale reaction with an aniline
acid-derived substrate was performed with reduced
photocatalyst loading. As a result, the reaction still proceeded
Table 3. Scope of alkenes for the deaminative Heck-type reaction.[a]
Table 2. Scope of Katritzky salts for the deaminative Heck-type reaction.[a,b]
Entry
1
Product 4 or 5
4ib: Ar = 4-FC6H4
Yield[b]
90%
89%
95%
78%
71%
68%
60%
66%[c]
93%
71%
77%
56%
65%
2
4ic: Ar = 4-ClC6H4
4id: Ar = 4-MeC6H4
4ie: Ar = 4-MeOC6H4
4if: Ar = 4-Me2NC6H4
4ig: Ar = 4-PhC6H4
4ih
3
4
5
6
7
8
4ai
9
5ia: Ar = Ph
10
11
12
13
5ib: Ar = 4-ClC6H4
5ic: Ar = 4-MeOC6H4
5id: Ar = 2-Thiophenyl
5ke
14
5af
40%
[a] Reaction conditions 1: see entry 7 in Table 1. [b] Isolated yield. [c] 1 (0.24
mmol), 2a (0.2 mmol). [d] Without DABCO. [e] Gram-scale reaction: 1m (2.29
g, 4.0 mmol), 2a (1.12 ml, 6.4 mmol), [Ir]-1 (1.5 mol%) in CH3CN (25 mL) at
40°C under an argon atmosphere and irradiation by 2x3 W blue LEDs for 48
h.
[a] Reaction conditions 1: see entry 7 in Table 1. [b] Isolated yield. [c] Using
trans-cinnamylic acid; E/Z ratio = 8:1.
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10.1002/anie.201813689
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COMMUNICATION
The carbonylative Heck reaction is an important method for
synthesizing α,β-unsaturated ketones.[15] However, this reaction
was limited to aryl or vinyl electrophilic reagents, with few
examples of carbonylative alkyl-Heck reactions.[16] Based on our
experience in photocatalytic radical carbonylation,[17] the
optimum conditions for the deaminative carbonylative Heck-type
reaction were quickly established. As shown in Table 4,
undergoes a C-N bond cleavage to form a stable pyridine
species (Tppy) and a reactive alkyl radical I. The addition of
radical I to alkene substrate 2 produces a new, more stable
carbon radical II. Finally, the single electron oxidation of II (Ar =
Ar' = Ph, E'1/2 = 0.31 V vs. SCE)[19a] by the oxidation state of the
photocatalyst (E1/2OX = 1.51 V vs. SCE)[19b] and the subsequent
deprotonation process produces the desired alkenylation
representative Katritzky salts prepared from primary alkylamines, product 3. For the carbonylative alkyl-Heck-type reaction, the
including linear and cyclic amines, successfully participated in
the designed reaction, affording the corresponding enone
products in 65-74% yields (Table 4). To our delight, the
Alogliptin-derived substrate was also successful for this
deaminative carbonyl Heck-type reaction with a good yield
(Table 4, 6oa: 65% yield).
alkyl radical I is first captured by the carbon oxide; then, the
generated acyl radical III reacts with the alkene to form a
relatively stable radical IV. The same oxidation/deprotonation
process affords the final enone product 4.
In summary, we have developed the first deaminative alkyl-
Heck-type reaction and deaminative carbonylative alkyl-Heck-
type reaction of primary alkylamines. The described protocol
represents a significant complement to the Pd-catalyzed, state-
of-the-art Heck reaction. A variety of alkene products were
obtained from readily available feedstock at room temperature
under visible light irradiation. The conversion of primary
alkylamines to Katritzky salts and the subsequent C-N activation
through a photocatalytic SER process were crucial to the
success of this approach. Furthermore, these two efficient
deaminative transformations successfully proved their synthetic
potential for structure modification of dipeptide or drug
molecules.
Table 4. Representative examples of the deaminative carboxylative Heck-type
reaction.[a,b]
Acknowledgements
We are grateful to the National Science Foundation of China (No.
21822103, 21820102003, 21772052, 21772053, 21572074 and
21472057), the Program of Introducing Talents of Discipline to
Universities of China (111 Program, B17019), the International
Joint Research Center for Intelligent Biosensing Technology and
Health, and the Natural Science Foundation of Hubei Province
(2017AHB047) for support of this research.
[a] Reaction condition 2: the same as entry 7 in Table 1 except argon was
replaced with CO (80 atm). [b] Isolated yield.
We then proposed a possible reaction mechanism for the
deaminative Heck-type reaction and its carboxylative variant
based on previous work[5-7,12a] and our preliminary mechanistic
investigations. As simply illustrated in Scheme 2, the [Ir(III)]
photocatalyst reaches an excited state ([Ir(III)]*) under the
illumination of blue LEDs and is then subsequently quenched by
the oxidative Katritzky salt 1 via a SER pathway. This process
was strongly supported by the results of the Stern-Volmer
fluorescence quenching experiment.[18] For the alkyl-Heck-type
reaction, the resultant unstable heteroaryl radical immediately
Keywords: Heck reaction • carbonylative Heck reaction •
deaminative transformation • visible light photocatalysis
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COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
COMMUNICATION
This work describes the first example
of deaminative alkyl-Heck-type
reaction and its carbonylative variant
through photocatalytic C-N bond
activation. This new protocol
represents a significant complement to
the classic Pd-catalyzed Heck reactions,
featuring easily available feedstock,
good reaction efficiency and mild
reaction conditions.
Xuan Jiang, Mao-Mao Zhang, Wei Xiong,
Liang-Qiu Lu* and Wen-Jing Xiao*
Page No. – Page No.
Deaminative (Carbonylative) Alkyl-Heck-
type Reactions Enabled by Photocatalytic
C-N Bond Activation
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