Catalyst-free Decarboxylation and Decarboxylative Giese Additions of Alkyl Carboxylates through Photoactivation of Electron Donor-Acceptor Complex

Article abstract of DOI:10.1002/adsc.201900803

We report herein a catalyst-free method to perform decarboxylative conjugated addition and hydrodecarboxylation of aliphatic N-(acyloxy)phthalimides (redox active esters, RAEs) through photoactivation of electron-donor-acceptor (EDA) complex with Hantzsch ester (HE) in N,N-dimethylacetamide (DMA) solution. The reactions present a green method to decarboxylatively construct carbon-carbon bond and to perform hydrodecarboxylation with broad substrate scope and functional group tolerance under mild blue light irradiation condition without recourse of popularly used photoredox catalysts. (Figure presented.).

Full text of DOI:10.1002/adsc.201900803

Title: Catalyst-free Decarboxylation and Decarboxylative Giese
Additions of Alkyl Carboxylates through Photoactivation of
Electron Donor-acceptor Complex
Authors: Chao Zheng, Guangzu Wang, and Rui Shang
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.201900803
Link to VoR: http://dx.doi.org/10.1002/adsc.201900803

10.1002/adsc.201900803
Advanced Synthesis & Catalysis
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Catalyst-free Decarboxylation and Decarboxylative Giese
Additions of Alkyl Carboxylates through Photoactivation of
Electron Donor-acceptor Complex
Chao Zheng,a,b Guang-Zu Wang,b and Rui Shangb,c*
a
Key Laboratory of Tropical Medicinal Plant Chemistry of Ministry of Education, Collaborative Innovation Center of
Tropical Biological Resources, Hainan Normal University, Haikou, Hainan 571158, China.
Department of Chemistry, University of Science and Technology of China, Hefei 230026, China.
Department of Chemistry, School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113- 0033,
b
c
Japan.
E-mail: rui@chem.s.u-tokyo.ac.jp
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
acceptor complex with an electron donor species
under irradiation.[10] The electron-donor-acceptor
complex can be a transient encounter complex, which
is formed in equilibrium in solution through weak
non-covalent interactions,[11] such as Coulombic
Abstract. We report herein a catalyst-free method to
perform decarboxylative conjugated addition and
hydrodecarboxylation
of
aliphatic
N-
(acyloxy)phthalimides (redox active esters, RAEs)
through photoactivation of electron-donor-acceptor
(EDA) complex with Hantzsch ester (HE) in N,N-
dimethylacetamide (DMA) solution. The reactions
present a green method to decarboxylatively construct
carbon-carbon bond and to perform hydrodecarboxylation
with broad substrate scope and functional group tolerance
under mild blue light irradiation condition without
recourse of popularly used photoredox catalysts.
interaction, hydrogen bonding, and π-
acking,
which are heavily affected by solvation. With our
interest in development of inexpensive methodologies
to use aliphatic carboxylic acids in organic
synthesis,[12] we conceived that decarboxylative
conjugated addition with Michael acceptors and
hydrodecarboxylation could be performed with a
electron donor substrate such as Hantzsch ester (HE)
under mild irradiation condition using blue LEDs. As
depicted in Figure 1, an encounter complex of RAE
and HE is photoactivated to induce inner sphere
electron transfer to decarboxylatively generate alkyl
radical. The alkyl radical can be effectively trapped
by an olefin acceptor to form a new carbon-carbon
bond followed by further hydrogen transfer from
oxidized HE to deliver conjugate addition product
and pyridinium salts. Hydrodecarboxylation can also
be achieved in the absence of olefin coupling partner.
Keywords: Decarboxylation; Giese Additions;
Photoactivation; Redox Active Ester; EDA complex
Decarboxylative carbon-carbon bond construction[1]
and efficient decarboxylation[2] are transformations
still receiving intensive developments in synthetic
community, because of the easy accessibility,
abundance, and environmentally benign properties of
aliphatic carboxylic acids for green organic
synthesis.[3] Besides the atom- and step-economic
methods to utilize carboxylic acids directly,[4] the
traceless activation group strategy that uses N-
(acyloxy)phthalimide (so-called redox active esters or
RAEs),[5] which can be easily installed through
condensation reaction,[5c] offered the other convenient
way
to
perform
various
decarboxylative
transformations.[6] The majority of the developed
methodologies for decarboxylative carbon-carbon
bond formation utilized either transition-metal
complexes as catalyst under thermal condition[7] or
photoredox catalysts[8] to activate RAEs, especially
for decarboxylative conjugated additions.[9] Recent
studies revealed that RAEs could be efficiently
activated through formation of electron-donor-
Figure 1. Working hypothesis of decarboxylative and
deaminative conjugate addition through photoactivation of
encounter EDA complex.
1
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10.1002/adsc.201900803
Advanced Synthesis & Catalysis
Herein we reveal a simple reaction system composed
of RAE (1.5 equiv), HE (1.5 equiv), and olefin
acceptor (1.0 equiv) in N,N-dimethylacetamide
solvent (DMA) under irradiation of blue LEDs
effectively delivers Giese type conjugate addition[13]
products with broad substrate scope of both
carboxylates and olefins. This method is also
applicable to deaminative conjugate addition of
primary aliphatic amine-derived Katritzky salt.[14,15]
Selection of DMA as solvent is a key to achieve high
reaction efficiency and broad reaction scope. It is
noteworthy that Overman and co-workers reported
The optimized reaction condition is shown in Table
1, entry 1. Irradiation of a mixture of phenyl acrylate
(0.1 mmol), N-(cyclohexanecarbonyl)phthalimide
(0.15 mmol), and HE (0.15 mmol) in DMA (2.0 mL)
by blue LEDs (456 nm) under room temperature (25
± 3 °C) for 12 h delivered Giese type addition
product (1) in 91% yield. The same reaction
condition is also applicable for deaminative Giese
addition using Katritzky salts (entry 2, see
Supplementary Information for key parameters of
deaminative addition).[15] Solvent is a key parameter
for this reaction as solvation heavily affects
molecular assembly through weak non-covalent
interaction to form encounter complex for
that
a
tertiary RAE (1-methylcyclohexane-1-
carboxylate) reacted with butanone and acrylonitrile
in moderate yields (50 – 60%) in the absence of a
photoredox catalyst.[16] The method presented herein
offers an environmentally benign and economic
method to perform decarboxylative addition and
photoactivation
(entries
3–6).
N,N-
dimethylacetamide (DMA) was found to be the
optimal solvent, while the yield significantly
decreased when N,N-dimethylformamide (DMF) was
used (entry 3). Tetrahydrofuran (THF), acetonitrile,
dichloromethane (DCM) used as solvent resulted in
much lower yields.
hydrodecarboxylation,
and
demonstrated
the
synthetic utility of photoactivation of electron-donor-
acceptor complex (EDA complex) with broad
substrate scope without using expensive photocatalyst.
Table 2. Scope of decarboxylative conjugated addition
Table 1. Optimization of reaction conditions.[a]
with respect to olefins.[a]
Entry
Variations from condition above
Yield [%]
91(88[b])
85
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
A, none
B, none
A, DMF instead of DMA
A, THF instead of DMA
68
42
33
A, CH3CN instead of DMA
A, DCM instead of DMA
A, TTMMS instead of HE
A, BNAH instead of HE
A, 1,4-CHD instead of HE
A, 390 nm instead of 456 nm
A, 427 nm instead of 456 nm
A, 440 nm instead of 456 nm
A, 467 nm instead of 456 nm
A or B, without HE
18
trace
25
n.r．
65
81
89
82
n.r.
71
86
A, HE (1.2 equiv)
A, HE (2 equiv)
17
18
19
20
A, H2O (1 equiv)
A or B, under air
A or B, in dark
85
trace
n.r.
n.r.
Cy-Cl/Br/I instead of A
[a]
Reaction condition: alkenes (0.2 mmol), RAEs (0.3
[a] Reaction condition: olefin (0.2 mmol), electrophiles (0.3
mmol), HE (0.3 mmol) in DMA (2 mL), irradiated by 40
W blue LEDs (456 nm) at room temperature for 12 h under
argon atmosphere. Yield determined by GC using
diphenylmethane as an internal standard. [b] Isolated yield.
TTMMS = Tris(trimethylsilyl)silane. BNAH = 1-benzyl-
1,4-dihydronicotinamide. 1,4-CHD = 1,4-cyclohexadiene.
mmol), HE (0.3 mmol) in DMA (2 mL), irradiated by 40W
blue LEDs (456 nm) at room temperature for 12 h under
argon atmosphere. Isolated yield.
Katritzky salt was used instead of RAE and yield was
determined by GC analysis using diphenylmethane as an
internal standard. [c] RAEs were used in 0.4 mmol.
[b]
The corresponding
2
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10.1002/adsc.201900803
Advanced Synthesis & Catalysis
Electron donor reagents other than HE, such as
tris(trimethylsilyl)silane (TTMMS), 1-benzyl-1,4-
unsaturated ester (2–4, 18), sulfone (5), nitrile (6),
aldehyde (7), amide (9, 10), phosphate (11), and
ketone (19). Maleate was also suitable substrate (8).
The reaction also worked well with vinyl silane and
vinyl pinacol boronate (12–14), albeit in moderate
yields. N-vinyl carbazole was amenable substrate to
deliver N-alkylated carbazole in moderate yield (15),
while vinyl alkyl ether did not afford the desired
addition product probably due to the competitive
radical oligomerization of vinyl ether (16). Ethyl
propiolate afforded β-alkylated acrylate as
stereoisomeric mixture (17). Substituents on both α–
and β– positions were tolerated (7, 8, 18, 20).
The reaction scope regarding to aliphatic
carboxylic acid derived RAEs is demonstrated in
Table 3. Primary alkylation, secondary alkylation,
and tertiary alkylation using RAEs all proceeded
smoothly in good yields. A cis-alkene structure in
oleic acid was full preserved (21). Alkyl bromide (23),
alkyl chloride (24), and terminal alkyne (25), which
are useful coupling units in cross-coupling
chemistry,[17] were well tolerated under this metal-
free condition. Amino acid derived RAEs were not
amenable under the optimized reaction conditions.
dihydronicotinamide
(BNAH),
and
1,4-
cyclohexadiene (1,4-CHD) were tested and were all
incompetent (entries 7–9). The wavelength length of
light source is a crucial parameter in irradiation-
induced reactions. As shown in entries 10-13, using
purple LEDs of wavelength of 390 nm resulted in
reduced yield. Other irradiation sources with
wavelengths of 427 nm, 440 nm, and 467 nm were
competent light sources that resulted in good yield
(>80%). Hantzsch ester (HE) is absolutely necessary
for both decarboxylative and deaminative additions
(entry 14), and reducing the amount of HE to 1.2
equivalent resulted in reduced yield (entries 15 and
16). The reaction is not sensitive to water (entry 17)
but is highly sensitive to oxygen. Reaction exposed to
air produced only trace amount of desired product
(entry 18). Irradiation by LED light is essential for
the reactivity (entry 19). Alkyl halides that do not
form absorbing EDA complex with HE could not be
activated by this method (entry 20). Critically
speaking, the necessity of stoichiometric amount of
HE to form absorbing EDA complex is
a
disadvantage of this method regarding to atom
economy.
Table 4. Decarboxylative reduction of RAEs using HE.[a]
Table 3. Scope of decarboxylative conjugate additions
with respect to different aliphatic carboxylic acids.[a]
[a]
Reaction condition: RAEs (0.2 mmol), HE (0.3 mmol)
in DMA (2 mL), irradiated by 40 W blue LEDs (456 nm)
at room temperature for 24 h under argon atmosphere.
Yield of isolated product.
We noticed in many entries of decarboxylative
addition in Table 2 and Table 3, the moderate yields
were due to formation of competitive reduction
product by hydrogen abstraction of alkyl radical with
oxidized HE (Figure 1). We realized that besides
decarboxylative addition to forge carbon-carbon bond,
the method also provides an efficient way for
hydrodecarboxylation of aliphatic carboxylic acids in
the absence of olefin coupling partners. Compared
with Barton decarboxylation,[18] which requires
handling of toxic and smelly tin and thiol reagents,
the metal-free method through visible light activation
of EDA complex present a user-friendly and
[a]
Reaction condition: olefines (0.2 mmol), RAEs (0.3
mmol), HE (0.3 mmol) in DMA (2 mL), irradiated by 40
W blue LEDs (456 nm) at room temperature for 12 h under
argon atmosphere. Yield of isolated product.
The scope of Giese type addition reaction
regarding to olefin part is demonstrated in Table 2.
Indan-2-carboxylic acid derived RAE was chosen as
model substrate for easily tracing the product under
thin layer chromatography. A broad scope of olefins
exhibited as amenable substrates, including α,β-
operationally
simple
way
for
reductive
decarboxylation. Primary, secondary, and tertiary
carboxylic acids-derived RAEs all decarboxylated
smoothly to deliver the reduction products in high
yields (Table 4, 33–36).
3
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10.1002/adsc.201900803
Advanced Synthesis & Catalysis
a.
Interestingly, amino acid derived RAEs (37, 38) were
not compatible substrates, probably because
hydrogen bonding of amide with HE disturbs the
formation of encounter EDA complex through π-π
assembly for productive photoactivation.
HE
RAE
HE + RAE
b.
Scheme 1. Evidence for radical decarboxylation.
Radical clock experiment[19] (Scheme 1, eq. 1) and
experiment using radical scavenger (Scheme 1, eq. 2)
unambiguously proved radical decarboxylation
process. The scalability of this method is
demonstrated by a gram-scale synthesis in good yield
(Scheme 2).
Figure 2. UV-vis spectra. (a) UV-vis spectra measured in
DMA solvent. Inset photo shows the appearance of
reactant solution under reaction concentration. (b) UV-vis
spectra measured in DCM solvent. Concentration of each
substance in UV-Vis measurement is identical to the
concentration used in reactions (c*).
O
HE (9.0 mmol)
PhO
PhO
NPhth
+
O
DMA (50 mL), rt, 24 h
blue LEDs (456 nm)
O
O
81% (1.13 g)
6.0 mmol
9.0 mmol
Scheme 2. Gram-scale synthesis.
In conclusion,
a
catalyst-free method for
UV-vis absorption spectrum of the reaction
mixture was measured to provide information on
formation of EDA complex. As shown in Figure 2a, a
mixture of RAE (A) and HE in DMA with a
concentration identical to the reaction condition
exhibits a strong bathochromic shift compared with
the absorption of each substrate alone. The absorption
band (red line) is considered to belong to the
formation of an EDA complex, and extends to
wavelength longer than 500 nm. Concentration plays
an important role, as a diluted solution (1/10 of the
concentration of the reaction mixture) showed blue-
shifted absorption band. This observed dilution effect
on hypsochromic shift of absorption band could be
ascribed to the inhibition of association process to
form EDA complex. Selection of solvent is crucial
for photoreaction proceeding through encounter EDA
complex, as solvation may heavily affect the transient
formation of EDA complex. As shown in Figure 2b,
the UV-vis absorption spectra measured in DCM (a
poor solvent afforded desired product in 18% yield in
Table 1) showed hypsochromic shift of all absorption
bands compared with spectra measured in DMA,
which suggests that the encounter EDA complex does
not form effectively in DCM.
hydrodecarboxylation and decarboxylative Giese
addition reaction based on photoactivation of
RAEs/HE encounter EDA complex is discovered.
Solvation effect that heavily affects the formation of
encounter EDA complex is find to be crucial for the
high reactivity and substrate generality. The reaction
exhibits high efficiency and broad substrate scope,
and offers a green and sustainable method to used
biomass-derived aliphatic carboxylic acids in organic
synthesis.
Experimental Section
General Procedure
Olefins (1.0 equiv, 0.2 mmol) (when solid), redox-active
esters (0.3 mmol), HE (0.3 mmol) were placed in a
transparent Schlenk tube equipped with a stirring bar. The
tube was evacuated and filled with argon (repeated for
three times). To these solids, olefins (1.0 equiv, 0.2 mmol)
(when liquid) and anhydrous DMA (2 mL) were added via
a gastight syringe under argon atmosphere. The reaction
mixture was stirred under irradiation with blue LEDs (456
nm, distance app. 3.0 cm from the bulb), maintained at
approximately room temperature by a desk fan in the air-
conditioned room of 25°C for 12 h. The mixture was then
quenched with saturated NaCl solution and extracted with
ethyl acetate (3 × 10 mL). The organic layers were
combined and concentrated under reduced atmospheric
pressure. The product was purified by flash column
4
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10.1002/adsc.201900803
Advanced Synthesis & Catalysis
chromatography on silica gel using petroleum ether/ethyl
acetate as eluent.
A. M. Olivares, A. M. Spiewak, K. A. Johnson, T. A.
DiBenedetto, S. Kim, L. K. Ackerman, D. J. Weix, J.
Am. Chem. Soc. 2016, 138, 5016–5019; c) F. Toriyama,
J. Cornella, L. Wimmer, T. G. Chen, D. D. Dixon, G.
Creech, P. S. Baran, J. Am. Chem. Soc. 2016, 138,
11132–11135; d) J. T. Edwards, R. R. Merchant, K. S.
McClymont, K. W. Knouse, T. Qin, L. R. Malins, B.
Vokits, S. A. Shaw, D. H. Bao, F. L. Wei, T. Zhou, M.
D. Eastgate, P. S. Baran, Nature 2017, 545, 213–218.
[8] a) J. Yang, J. Zhang, L. Qi, C. Hu, Y. Chen, Chem.
Commun. 2015, 51, 5275–5278; b) W.-M. Cheng, R.
Shang, Y. Fu, ACS Catal. 2016, 7, 907–911; c) W. M.
Cheng, R. Shang, M. C. Fu, Y. Fu, Chem. Eur. J. 2017,
23, 2537–2541; d) K. Xu, Z. Tan, H. Zhang, J. Liu, S.
Zhang, Z. Wang, Chem. Commun. 2017, 53, 10719–
10722; e) W. Kong, C. Yu, H. An, Q. Song, Org. Lett.
2018, 20, 349–352.
[9] a) M. J. Schnermann, L. E. Overman, J. Am. Chem. Soc.
2011, 133, 16425–16427; b) M. J. Schnermann, L. E.
Overman, Angew. Chem. Int. Ed. 2012, 51, 9576–9580;
Angew. Chem. 2012, 124, 9714–9718; c) G. L. Lackner,
K. W. Quasdorf, L. E. Overman, J. Am. Chem. Soc.
2013, 135, 15342–15345; d) L. Chu, C. Ohta, Z. Zuo,
D. W. C. MacMillan, J. Am. Chem. Soc. 2014, 136,
10886–10889; e) G. Z. Wang, R. Shang, W. M. Cheng,
Y. Fu, Org. Lett. 2015, 17, 4830–4833; f) J. Schwarz, B.
König, Green Chem. 2016, 18, 4743–4749.
[10] a) L. Candish, M. Teders, F. Glorius, J. Am. Chem.
Soc. 2017, 139, 7440–7443; b) A. Fawcett, J. Pradeilles,
Y. Wang, T. Mutsuga, E. L. Myers, V. K. Aggarwal,
Science 2017, 357, 283–286; c) M.-C. Fu, R. Shang, B.
Zhao, B. Wang, Y. Fu, Science 2019, 363, 1429–1434.
[11] a) J. K. Kochi, Angew. Chem. Int. Ed. 1988, 27,
1227–1266; Angew. Chem. 1988, 100, 1331–1372; b) S.
V. Rosokha, J. K. Kochi, Acc. Chem. Res. 2008, 41,
641–653.
[12] a) G. Z. Wang, R. Shang, Y. Fu, Org. Lett. 2018, 20,
888–891 b) C. Zheng, W.-M. Cheng, H.-L. Li, R.-S. Na,
R. Shang, Org. Lett. 2018, 20, 2559–2563; c) W. M.
Cheng, R. Shang, Y. Fu, Nat. Commun. 2018, 9, 5215.
[13] a) B. Giese, Angew. Chem. Int. Ed. 1983, 22, 753-
764; Angew. Chem. 1983, 95, 771-782; b) B. Giese, J.
A. González‐Gómez, T. Witzel, Angew. Chem. Int.
Ed. 1984, 23, 69–70; Angew. Chem. 1984, 96, 51–52;
c) G. Goti, B. Bieszczad, A. Vega ‐ Peñaloza, P.
Melchiorre, Angew. Chem. Int. Ed. 2019, 58, 1213–
1217; Angew. Chem. 2019, 131, 1226–1230; d) T. van
Leeuwen, L. Buzzetti, L. A. Perego, P. Melchiorre,
Angew. Chem. Int. Ed. 2019, 58, 4953–4957; Angew.
Chem. 2019, 131, 5007–5011.
Acknowledgements
This research was funded by the National Natural Science
Foundation of China (NSFC) (Grant No. 21702039), Key
Research and Development Program of Hainan Province (No.
ZDYF2019155), the Program for Innovative Research Team in
University (No. IRT-16R19). G.-Z.W. thanks China Postdoctoral
Science Foundation (2018M640588) for support.
References
[1] a) L. J. Goossen, G. Deng, L. M. Levy, Science 2006,
313, 662–664; b) R. Shang, Z. W. Yang, Y. Wang, S. L.
Zhang, L. Liu, J. Am. Chem. Soc. 2010, 132, 14391–
14393; c) N. Rodriguez, L. J. Goossen, Chem. Soc. Rev.
2011, 40, 5030–5048; d) R. Shang, L. Liu, Sci. China:
Chem. 2011, 54, 1670–1687; e) Y. Wei, P. Hu, M.
Zhang, W. Su, Chem. Rev. 2017, 117, 8864–8907; f) J.
Schwarz, B. König, Green Chem. 2018, 20, 323–361;
g) V. R. Yatham, P. Bellotti, B. König, Chem. Commun.
2019, 55, 3489–3492.
[2] a) D. H. Barton, J. C. Jaszberenyi, D. Tang,
Tetrahedron Lett. 1993, 34, 3381–3384; b) K.
Yamaguchi, Y. Kazuta, H. Abe, A. Matsuda, S. Shuto,
J. Org. Chem. 2003, 68, 9255–9262; c) E. J. Ko, G. P.
Savage, C. M. Williams, J. Tsanaktsidis, Org. Lett.
2011, 13, 1944–1947; d) T. Qin, L. R. Malins, J. T.
Edwards, R. R. Merchant, A. J. Novak, J. Z. Zhong, R.
B. Mills, M. Yan, C. Yuan, M. D. Eastgate, P. S. Baran,
Angew. Chem. Int. Ed. 2017, 56, 260–265; Angew.
Chem. 2017, 129, 266–271.
[3] a) A. J. Straathof, Chem. Rev., 2014, 114, 1871–1908;
b) J. Xuan, Z.-G. Zhang, W.-J. Xiao, Angew. Chem. Int.
Ed. 2015, 54, 15632–15641; Angew. Chem. 2015, 127,
15854–15864.
[4] a) Z. Zuo, D. T. Ahneman, L. Chu, J. A. Terrett, A. G.
Doyle, D. W. MacMillan, Science 2014, 345, 437–440;
b) Z. Zuo, D. W. MacMillan, J. Am. Chem. Soc. 2014,
136, 5257–5260; c) T. Chinzei, K. Miyazawa, Y. Yasu,
T. Koike, M. Akita, RSC Adv., 2015, 5, 21297–21300;
d) C. P. Johnston, R. T. Smith, S. Allmendinger, D. W.
MacMillan, Nature 2016, 536, 322–325; e) N. P.
Ramirez, J. C. Gonzalez-Gomez, Eur. J. Org. Chem.
2017, 2154–2163. f) V. R. Yatham, P. Bellotti, B.
König, Chem. Commun. 2019, 55, 3489–3492.
[5] a) K. Okada, K. Okamoto, M. Oda, J. Am. Chem. Soc.
1988, 110, 8736–8738; b) K. Okada, K. Okamoto, N.
Morita, K. Okubo, M. Oda, J. Am. Chem. Soc. 1991,
113, 9401–9402; c) G. H. L. Nefkens, G. I. Tesser, J.
Am. Chem. Soc. 1961, 83, 1263–1263; d) D. S. Muller,
N. L. Untiedt, A. P. Dieskau, G. L. Lackner, L. E.
Overman, J. Am. Chem. Soc. 2015, 137, 660–663. e) T.
Qin, J. Cornella, C. Li, L. R. Malins, J. T. Edwards, S.
Kawamura, B. D. Maxwell, M. D. Eastgate, P. S. Baran,
Science 2016, 352, 801–805.
[14] a) C. H. Basch, J. Liao, J. Xu, J. J. Piane, M. P.
Watson, J. Am. Chem. Soc. 2017, 139, 5313–5316; b) F.
J. R. Klauck, M. J. James, F. Glorius, Angew. Chem. Int.
Ed. 2017, 56, 12336–12339; Angew. Chem. 2017, 129,
12505–12508; c) S. Plunkett, C. H. Basch, S. O.
Santana, M. P. Watson, J. Am. Chem. Soc. 2019, 141,
2257–2262; d) H. Yue, C. Zhu, L. Shen, Q. Geng, K. J.
Hock, T. Yuan, L. Cavallo, M. Rueping, Chem. Sci.
2019, 10, 4430–4435.
[6] S. Murarka, Adv. Synth. Catal. 2018, 360, 1735–1753.
[7] a) J. Cornella, J. T. Edwards, T. Qin, S. Kawamura, J.
Wang, C. M. Pan, R. Gianatassio, M. Schmidt, M. D.
Eastgate, P. S. Baran, J. Am. Chem. Soc. 2016, 138,
2174–2177; b) K. M. Huihui, J. A. Caputo, Z. Melchor,
[15] Duing the scope investigation of this work Aggarwal
and co-workers reported the deaminative conjugate
addition using same strategy, so the scope of
5
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10.1002/adsc.201900803
Advanced Synthesis & Catalysis
deaminative conjugate addition was not further
[18] D. H. Barton, D. Crich, W. B. Motherwell, J. Chem.
Soc. Chem. Commun. 1983, 939–941.
[19] a) D. Griller, K. U. Ingold, Acc. Chem. Res.1980, 139,
317–323; b) G. Z. Wang, R. Shang, W. M. Cheng, Y.
Fu, J. Am. Chem. Soc. 2017, 139, 18307–18312.
demonstrated in this paper. For deaminative conjugate
addition using similar strategy, see: J. Wu, P. S. Grant,
X. Li, A. Noble, V. K. Aggarwal, Angew. Chem. Int.
Ed. 2019, 58, 5697–5701; Angew. Chem. 2019, 131,
5753–5757.
[16] G. Pratsch, G. L. Lackner, L. E. Overman, J. Org.
Chem. 2015, 80, 6025–6036.
[17] a) M. Nakamura, K. Matsuo, S. Ito, E. Nakamura, J.
Am. Chem. Soc. 2004, 126, 3686–3687; b) G.-Z. Wang,
R. Shang, Y. Fu, Synthesis 2018, 50, 2908–2914; c) A.
Hazra, M. T. Lee, J. F. Chiu, G. Lalic, Angew. Chem.
Int. Ed. 2018, 57, 5492–5496; Angew. Chem. 2018, 130,
5590–5594.
6
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10.1002/adsc.201900803
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