Visible-light-initiated manganese-catalyzed Giese addition of unactivated alkyl iodides to electron-poor olefins

Article abstract of DOI:10.1039/c9cc06400a

Herein, we report a mild protocol for direct visible-light-initiated Giese addition of unactivated alkyl iodides to electron-poor olefins (Michael acceptors) with catalysis by decacarbonyl dimanganese, Mn₂(CO)₁₀, an inexpensive earth-abundant-metal catalyst. This protocol is compatible with a wide array of sensitive functional groups and has a broad substrate scope with regard to both the alkyl iodide and the Michael acceptor.

Full text of DOI:10.1039/c9cc06400a

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DOI: 10.1039/C9CC06400A
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Visible-Light-Initiated Manganese-Catalyzed Giese Addition of
Unactivated Alkyl Iodides to Electron-Poor Olefins
Jianyang Dong, a Xiaochen Wang, a Zhen Wang, a Hongjian Song, a Yuxiu Liu a and Qingmin Wang*a,b
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
challenge is posed by the fact that the excited state of typical
photoredox catalysts cannot be efficiently quenched by unactivated
alkyl iodides (ca. −1.67 V vs. SCE for ethyl iodide) to generate alkyl
radicals.12
Herein, we report a mild protocol for direct visible-light-initiated Giese
addition of unactivated alkyl iodides to electron-poor olefins (Michael
acceptors) with catalysis by decacarbonyl dimanganese, Mn2(CO)10, an
inexpensive earth-abundant-metal catalyst. This protocol is compatible
with a wide array of sensitive functional groups and has a broad substrate
scope with regard to both the alkyl iodide and the Michael acceptor.
Therefore, we became interested in exploring the possibility of a
visible-light-initiated
manganese-catalyzed
Giese
reaction.
Mn2(CO)10, an inexpensive and readily available decacarbonyl
complex of an earth-abundant metal, can homolyze to form a
manganese-centered radical, [.Mn(CO)5], upon irradiation with
visible light,13 and the radical can selectively abstract the iodide
atom from an alkyl iodide to furnish an alkyl radical with
concomitant formation of Mn(CO)5I.14 For successful catalytic
turnover, the active catalyst, [·Mn(CO)5], would have to be
regenerated from Mn(CO)5I under the reaction conditions. Giese
reactions via such a process would be independent of the reduction
potential of the photoredox catalyst and would differ from all of the
photoredox Giese reactions shown in Scheme 1a. Herein we
disclose the successful development of a protocol for efficient
visible-light-initiated Giese reactions of unactivated alkyl iodides
with catalysis by Mn2(CO)10 via a unique mechanism (Scheme 1b).
The scope of the reaction was extended to alkyl iodides generated
from alcohols, which further demonstrates the versatility of our
protocol.
Modular organic reactions that form C(sp3)–C(sp3) bonds facilitated
by traceless activation groups are a useful addition to the medicinal
chemistry toolbox and have accelerated the discovery of new
therapeutics.1 One such reaction is the Giese addition, in which an
electron-deficient alkene is attacked by a nucleophilic alkyl radical.2
Classic Giese reactions using alkyl iodides as the alkyl radical source
often require a tin reagent, which can limit their substrate scope
and chemoselectivity.2,3 With the rapidly growing interest in the use
of photoredox catalysis in organic synthesis,4 there have been
several reports of visible-light-mediated photoredox Giese reactions
with carboxylic acids,5 alkyltrifluoroborates,6 alcohols,7 alkyl
bromides,8 and organotrimethylsilanes9 as the alkyl radical sources
(Scheme 1a).10 In addition, Ryu described a protocol for Giese
reaction with alkyl iodides under a Pd/light system using SolarBox
(1500 W of xenon lamp in a box).11 Although these reactions allow
access to diverse products, most of the previously reported
protocols require a precious-metal catalyst (Ir or Ru) and are limited
in scope with respect to the alkyl radical source. Therefore, it would
be a significant advance if the expensive Ir and Ru catalysts could be
replaced with an inexpensive, earth-abundant 3d transition metal,
such as Mn, and if the substrate scope could be expanded to widely
available organic compounds commonly used as building blocks in
medicinal chemistry, such as alcohols and alkyl iodides. However, a
a)
Current visible-light-mediated Giese reaction:
O
R
R
R
CO2H
Br
BF3K
O
R
OX
R
X = H or Npth
SiMe3
O
EWG
EWG
R
photoredox catalyst Ir/Ru
b) This work:
visible-light-mediated Giese reaction using unactivated alkyl iodides
Mn[0]
EWG
visible light
EWG
+
R
I
Mn
R
1o, 2o, 3o
a. State Key Laboratory of Elemento-Organic Chemistry, Research Institute of
Elemento-Organic Chemistry, Nankai University, Tianjin 300071, People’s
Republic of China. E-mail: wangqm@nankai.edu.cn, wang98@263.net
b. Collaborative Innovation Center of Chemical Science and Engineering (Tianjin),
Tianjin 300071, People’s Republic of China
inexpensive, abundant metal (Mn) catalyst
Scheme 1. Visible-light-mediated Giese reactions to form C–C
bonds.
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
Table 1. Optimization of reaction conditions.a
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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I
low yield of 14 may be due to the lower activity of benzyl radical.
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photocatalyst (10 mol %)
O
Ph
O
Ph
Notably, the Giese reaction of 4-iodophenyDleOtIh: y10l .i1o0d3i9d/eC,9wCCh0ic6h40h0aAs
an iodoaryl moiety, proceeded chemoselectively at the C(sp3)–I
bond to furnish 17 (68% yield). Remarkably, sunlight, the main
component of which is visible light, gave 17 in almost the same
yield (62%) as that obtained upon irradiation with a 36 W blue LED.
Unactivated secondary alkyl iodides generate more-stable radicals
than primary iodides and therefore gave higher yields of the
corresponding products (18–24). Finally, the use of tert-butyl iodide
enabled direct construction of compound 25 (82% yield), which has
a quaternary carbon. Likewise, this protocol provided access to 26,
a compound bearing an adamantyl moiety, which is often used by
medicinal chemists to enhance the druglike qualities of lead
compounds without increasing their toxicity.16
+
HE (1.5 equiv), solvent (0,1 M)
36 W blue LED, r.t.
O
O
1
2
3
entry
1
2d
3e
4e
5
photocatalyst
solvent
DMSO
DMSO
DMSO
DMSO
CH3CN
MeOH
DMA
yield (%)b
96 (92c)
82
Mn2(CO)10
Mn(CO)5I
[Ru(bpy)3](PF6)2
NR
Ir[dF(CF3)ppy]2(dtbbpy)PF6
Mn2(CO)10
Mn2(CO)10
Mn2(CO)10
Mn2(CO)10
—
NR
83
6
87
7
34
Table 2. Substrate scope with respect to the alkyl iodide.a
8f
DMSO
DMSO
DMSO
DMSO
NR
Mn2(CO)10 (10 mol %)
O
Ph
R
O
Ph
+
R
I
O
HE (1.5 equiv), DMSO (0,1 M)
36 W blue LED, r.t. 24 h
O
4-26
9
NR
1
1.0 equiv
2.0 equiv
10g
11h
Mn2(CO)10
Mn2(CO)10
NR
Primary alkyl radicals
Ph
O
Ph
Ph
O
Ph
O
O
Ph
O
80
O
O
O
4
, 70%
5
6
7
, 73%
, 63%
, 73%
aGeneral conditions, unless otherwise noted: 1 (0.3 mmol), 2 (0.6
mmol), photocatalyst (0.03 mmol), Hantzsch ester (HE, 0.45 mmol),
O
O
Ph
O
O
Ph
F3C
I
O
O
O
Ph
O
CF3
Cl
b
1
and solvent (3 mL) under Ar atmosphere. Determined by H NMR
spectroscopy using dibromomethane as an internal standard. NR =
no reaction. cIsolated yield. dCatalyst loading increased to 0.06
8
9
10
14
11
15
, 51%
,32%
, 52%
, 73%
O
Ph
Ph
O
Ph
O
Ph
O
Ph
Ph
Si
O
Ph
O
O
O
CO2Et
12
e
mmol. Catalyst loading reduced to 0.003 mmol. fPerformed in the
13
, 58%
, 62%
, 29%
, 77%
Secondary alkyl radicals
Ph
absence of light. gPerformed in the absence of HE. hReaction
mixture irradiated for 5 min and then kept in the dark for 24 h.
O
O
O
O
O
I
Ph
O
Ph
O
Ph
O
17
,68%
62% (sunshine)
18
, 80%
19
,75%
16
, 71%
O
We began our evaluation of Mn2(CO)10 as a catalyst for visible-
light-induced Giese addition by using iodocyclohexane (2, 2.0 equiv)
and benzyl acrylate (1, 1.0 equiv) as substrates (Table 1). We were
delighted to find that in the presence of 10 mol % of Mn2(CO)10 and
Hantzsch ester (HE) as a reductant, irradiation of a DMSO solution
of 1 and 2 with a 36 W blue LED at room temperature afforded an
excellent yield of addition product 3 (entry 1). Notably, Mn(CO)5I
could also mediate this reaction, affording 3 in 82% yield (entry 2),
which confirms that the active catalyst, [·Mn(CO)5], was generated
by visible-light irradiation of Mn(CO)5I. The reaction failed to
proceed if Mn2(CO)10 was replaced with a Ru or Ir photocatalyst
(entries 3 and 4). Other solvents (acetonitrile, methanol, and N,N-
dimethylaniline) gave lower yields than DMSO (entries 5–7). Control
experiments showed that the reaction did not occur in the absence
of light, Mn2(CO)10, or HE (entries 8–10). Unlike typical
photocatalysts, the Mn catalyst did not require a photon for
turnover (entry 11).14,15 However, continuous irradiation was
necessary for high efficiency, likely because the precatalyst,
Mn2(CO)10, was in equilibrium with the active catalyst, [·Mn(CO)5].
Also noteworthy is that unactivated primary, secondary, and
tertiary alkyl bromides and alkyl chlorides, as well as aryl iodides,
showed no reactivity.
With the optimized reaction conditions in hand, we studied the
scope of the reaction with respect to the unactivated alkyl iodide
(Table 2). We found that a wide range of primary alkyl iodides
reacted with 1 to give the desired products in moderate to good
yields. For example, linear alkyl iodides afforded 4–7 in 63–73%
yields. We were pleased to find that primary alkyl iodides bearing
various functional groups (chloride, iodide, trifluoromethyl, ethyl
ester, and trimethylsilyl) were amenable to the reaction conditions,
giving good yields of 8–13, respectively. Benzyl iodide, phenylethyl
iodide, and phenylpropyl iodide were also suitable substrates,
giving 14, 15, and 16 in 29%, 77%, and 71% yields, respectively. The
O
Ph
O
Ph
O
Ph
O
O
73%
O
Ph
O
20
,61%
21,
22
23
, 75%
, 74%
Tertiary alkyl radicals
Ph
O
O
Ph
O
Ph
O
O
O
24
, 74%
25
, 82%
26
,80%
aReactions were performed on a 0.3 mmol scale under the
optimized conditions shown in Table 1. Isolated yields are given.
Next, we tested this new Giese reaction protocol with a variety of
Michael acceptors and several alkyl iodides (Table 3). The mild
reaction conditions were found to be compatible with a range of
functional groups (esters, an alcohol, amides, imides, ethers, and a
sulfone), providing a variety of handles for subsequent synthetic
manipulations. Specifically, as far as acrylate-based acceptors,
unsubstituted acrylates and α-alkyl acrylates were well tolerated,
giving 27–33 in 34–95% yields. A cyclic ester acceptor gave the
corresponding product (34) in 41% yield. In addition, other
electrophilic olefins (alkylidene malonate, maleimide, phenyl
acrylamide, and phenyl vinyl sulfone) furnished the corresponding
conjugate adducts (35–41) in moderate ·to good yields (39–72%).
Taken together, the results shown in Tables 2 and 3 demonstrate
the robustness of this protocol.
To demonstrate the practicality of our method, we extended the
reaction to alkyl iodides generated from alcohols. Gratifyingly, we
found that pretreatment of naturally occurring secondary alcohols
L-menthol and steride with I2 generated the corresponding
iodoalkanes, which could then be subjected to our standard Giese
reaction conditions to furnish conjugate adducts 42 and 43,
respectively, in moderate yields (Scheme 2a).
2 | J. Name., 2012, 00, 1-3
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Table 3. Substrate scope with respect to the Michael acceptor.a
of HE-d2 led to >99% deuterium incorporation into pVrioewduAcrtticl3e.OTnhlinies
Mn2(CO)10 (10 mol %)
R
result indicates that HE was the only hydrogen source. Moreover, a
DOI: 10.1039/C9CC06400A
+
R
I
EWG
EWG
27-41
HE (1.5 equiv), DMSO (0,1 M)
36 W blue LED, r.t. 24 h
light/dark experiment showed that coupling product 3 could be
formed in the dark (see SI), which suggests that radical chain
propagation was involved in the reaction.
2.0 equiv
1.0 equiv
O
O
O
O
O
O
O
Ph
radical inhabitor yield
O
Ph
O
I
N
O
a)
Mn2(CO)10 (10 mol%)
27
31
28
32
29
33
30
TEMPO
Ph
, 95%
, 74%
, 95%
, 84%
,34%
NR
NR
O
Ph
O
Ph
+
HEH (1.5 equiv), DMSO (0,1M)
36 W blue LED, r.t. 24h
O
1
48
O
Ph
3
O
2
O
Boc
N
O
O
detected by HRMS
O
Ph
CO2Et
b)
I
O
O
Mn2(CO)10 (10 mol%)
CO2Et
+
CO2Et
OH
, 51%
EtO2C
HEH (1.5 equiv), DMSO (0,1M)
36 W blue LED, r.t. 24h
CO2Et
51, 36%
, 58%
34
, 41%
49
50
trans/cis = 4:1
trans/cis = 58/42
O
Ph
Ph
Mn2(CO)10 (10 mol%)
H
N
O
Ph
O
O
O
+
CO2Et
O
O
O
I
Ph
HEH (1.5 equiv), DMSO (0,1M)
36 W blue LED, r.t. 24h
N
O
1
Ph
N
EtO2C
53b
O
O
52
Ph
53a
57%
9:1
Ph
, 56%
35
36
37
, 55%
,39%
38
, 69%
Scheme 3. Mechanistic experiments.
Boc
O
N
H
N
O
H
N
Ph
Ph
SO2Ph
, 72%
O
On the basis of our experimental observations and literature
reports, we propose the mechanism depicted in Scheme 4. First,
Mn2(CO)10 is homolyzed to [.Mn(CO)5] upon irradiation with the
blue LED. Subsequent iodine abstraction from iodocyclohexane (2)
O
39
40
41
, 47%
, 53%
aReactions were performed on a 0.3 mmol scale under the
optimized conditions shown in Table 1. Isolated yields are given.
generates nucleophilic radical species
A and Mn(CO)5I; this
In addition, the protocol was amenable to scale up: the reaction
of 1 with 44 carried out on a 4.0 mmol scale under sunlight was
complete within 6 h and gave 17 in 56% yield (Scheme 2b). Iodide
17 smoothly underwent Suzuki coupling with arylboronic acids to
provide moderate to good yields of the corresponding products
abstraction step is effectively irreversible owing to the difference in
bond dissociation energy between the Mn–I bond of Mn(CO)5I (67
kcal/mol) and the C(sp3)–I bond of iodocyclohexane (60 kcal/mol).13
Radical A then adds to Michael acceptor 1 via a Giese-type pathway
to afford radical intermediate B. This intermediate abstracts a
hydrogen from the 4-position of the HE to give product 3 and a
dienyl radical, which reacts with Mn(CO)5I to regenerate the active
catalyst, [.Mn(CO)5].
(45–47).
(a) Use of alcohols for Giese reaction
1) I2, PPh3, imidazole, DCM
O
Ph
2) Standard conditions
OH
O
42
, 67%
L-menthol
Ph
(CO)5Mn-Mn(CO)5
I
O
H
1) I2, PPh3, imidazole, DCM
2) Standard conditions
H
H
O
hv
H
H
HO
H
43
, 40%
steride
(b) Gram-scale reaction, functionalization of iodide
Ph
Mn(CO)5
2
17
O
EtO2C
EtO2C
CO2Et
CO2Et
Mn2(CO)10 (10 mol%)
O
I
Ph
I
+
O
HE (1.5 equiv), DMSO (0,1M)
sunshine, r.t. 24 h
O
I
N
17
, 0.88 g, 56%
1
44
H
I
A
O
O
Ph
Ph
O
Ph
ArB(OH)2, Pd(OAc)2
K2CO3, PPh3
,
O
O
45
,69%
O
1
O
toluene, EtOH, H2
100 o
O
C
O
Ph
N
H
46
,65%
47
, 1.1g, 60%
I-Mn(CO)5
+
Scheme 2. Applications of the protocol.
O
Ph
H
O
Ph
O
Having explored the substrate scope and utility of the reaction,
we turned our attention to the mechanism (Scheme 3). When a
radical scavenger, 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) or
1,1-diphenylethylene, was present in a reaction mixture containing
1 and 2, the formation of 3 was completely inhibited; instead the
product of cyclohexyl radical trapping, 1-(cyclohexyloxy)-2,2,6,6-
tetramethylpiperidine (48), was detected by mass spectrometry
(Scheme 3a). To confirm the involvement of radical species (Scheme
3b), we carried out a radical clock experiment: reaction of
(iodomethyl)cyclopropane (50) with ethyl acrylate (49) gave 1,2-
disubstituted cyclopentane 51 in 36% yield. The reaction of 6-iodo-
1-hexene (52) and 1 gave 9:1 mixture of 53a and 53b in 57% yield
via a 5-exo radical cyclization. These experiments clearly point to a
radical pathway. Finally, to confirm the source of the hydrogen
atom in the product, we performed two deuterium-labeling
experiments (Figure S6). Although the reaction of 1 and 2 in DMSO-
d6 resulted in a coupled product containing no deuterium, the use
EtO2C
CO2Et
B
3
O
N
H
Scheme 4. Proposed mechanism
Conclusions
In conclusion, we have developed a protocol for visible-light-
initiated Giese reactions involving unactivated alkyl iodides with
catalysis by Mn2(CO)10, an inexpensive complex of an earth-
abundant metal. This versatile protocol tolerates a wide range of
functional groups and has a broad scope with regard to both the
alkyl iodide and the Michael acceptor. The reaction was also
extended to alkyl iodides generated from alcohols, further
demonstrating the versatility of our method. Moreover, unlike the
tin hydride catalyzed reaction originally reported by Giese, this
reaction was chemoselective for a C(sp3)–I bond over C(sp3)–X (X =
This journal is © The Royal Society of Chemistry 20xx
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Br, Cl) bonds and C(sp2)–I bonds. We believe that this novel
protocol will facilitate the development of clinical drug candidates.
This work is supported by the National Key Research and
Development Program of China (2018YFD0200100), the National
Natural Science Foundation of China (21732002, 21672117,
21772102) and the Ph.D. Candidate Research Innovation Fund of
the College of Chemistry Nankai University.
9
(a) Y. Zhao, J.-R. Chen, W.-J. Xiao, Org. Lett. 2016, 18, 6304;
(b) L. R. Espelt, I. S. McPherson, E. M.DWOIi:e1n0s.1c0h3,9VTi/eC.w9PAC.rtCiYc0ole6oO4nn0,l0inJAe.
Am. Chem. Soc. 2015, 137, 2452; (c) K. Nakajima, M.
Kitagawa, Y. Ashida, Y. Miyake, Y. Nishibayashi, Chem.
Commun. 2014, 50, 8900; (d) C. Levpque, L. Chenneberg, V.
Corce, C. Ollivier, L. Fensterbank, Chem. Commun. 2016, 52,
9877; (e) M. Silvi, C. Verrier, Y. P. Rey, L. Buzzetti, P.
Melchiorre, Nat. Chem. 2017, 9, 868.
10 (a) R. Zhou, H. Liu, H. Tao, X. Yu, J. Wu, Chem. Sci. 2017, 8,
4654; (b) D. Ravelli, M. Zoccolillo, M. Mella, M. Fagnoni, Adv.
Synth. Catal. 2014, 356, 2781; (c) X. Liu, X. Ye, F. Burese, H.
Liu, Z. Jiang, Angew. Chem. Int. Ed. 2015, 54, 11443; (d) L.
Ruiz Espelt, E. M. Wiensch, T. P. Yoon, J. Org. Chem. 2013,
78, 4107; (e) S. Kamijo, G. Takao, K. Kamijo, T. Tsuno, K.
Ishiguro, T. Murafuji, Org. Lett. 2016, 18, 4912; (f) J. A.
Terrett, M. D. Clift, D. W. C. MacMillan, J. Am. Chem. Soc.
2014, 136, 6858; (g) W. Yuan, Z. Zhou, L. Gong, E. Meggers,
Chem. Commun. 2017, 53, 8964; (h) A. Gualandi, D.
Mazzarella, A. Ortega-Martinez, L. Mengozzi, F. Calcinelli, E.
Matteucci, F. Monti, N. Armaroli, L. Sambri, P. G. Cozzi, ACS
Catal. 2017, 7, 5357; (i) X.-J. Tang, Z. Zhang, W. R. Jr. Dolbier,
Chem. Eur. J. 2015, 21, 18961. (j) T. Leeuwen, L. Buzzetti, L. A.
Perego and P. Melchiorre, Angew. Chem. Int. Ed. 2019, 58,
4953; (k) J. Wu, P. S. Grant, X. Li, A. Noble and V. K. Aggarwal,
Angew. Chem. Int. Ed. 2019, 17, 5753.
Conflicts of interest
There are no conflicts to declare.
Notes and references
1
2
(a) T. Cernak, K. D. Dykstra, S. Tyagarajan, P. Vachal, S. W.
Krska, Chem. Soc. Rev., 2016, 45, 546; (b) S. D. Roughley, A.
M. Jordan, J. Med. Chem., 2011, 54, 3451; (c) A. M. Jordan, S.
D. Roughley, Drug Discovery Today, 2009, 14, 731; (d) J. S.
Carey, D. Laffan, C. Thomson, M. T. Williams, Org. Biomol.
Chem., 2006, 4, 2337.
(a) B. Giese, J. Dupuis, Angew. Chem. Int. Ed. 1983, 22, 622;
(b) B. Giese, Angew. Chem. Int. Ed. 1983, 22, 753; (c) B.
Giese, J. A. Gonzalez-Gomez, T. Witzel, Angew. Chem. Int. Ed.
1984, 23, 69. （d）S. Ni, A. F. Garrido-Castro, R. R. Merchant,
J. N. deGruyter, D. C. Schmitt, J. J. Mousseau, G. M. Gallego,
S. Yang, M. R. Collins, J. X. Qiao, K.-S. Yeung, D. R. Langley, M. 11 (a) S. Sumino and I. Ryu, Org. Lett. 2016, 18, 52; (b) A.
A. Poss, P. M. Scola, T. Qin, P. S. Baran, Angew. Chem. Int. Ed.
2018, 57, 14560; (e) S. Han, S. Liu, L. Liu, L. Ackermann, J. Li,
Org. Lett. 2019, 21, 5387; (f) K. M. M. Huihui, R. Shrestha, D.
J. Weix, Org. Lett. 2017, 19, 340; (g) J. Wang, H. Lundberg, S.
Asai, P. Martín-Acosta, J. S. Chen, S. Brown, W. Farrell, R. G.
Dushin, C. J. O’Donnell, A. S. Ratnayake, P. Richardsonc, Z.
Fusano, S. Sumino, S. Nishitani, T. Inouye, K. Morimoto, T.
Fukuyama, I. Ryu, Chem. - Eur. J. 2012, 18, 9415; (c) S.
Sumino, T. Ui, I. Ryu, Org. Lett. 2013, 15, 3142; (d) S. Sumino,
T. Ui, I. Ryu, Org. Chem. Front. 2015, 2, 1085; (e) S. Sumino,
T. Ui, Y. Hamada, T. Fukuyama, I. Ryu, Org. Lett. 2015, 17,
4952.
Liu, T. Qin, D. G. Blackmond, P. S. Baran, PNAS, 2018, 115, 12 (a) A. J. Fry, R. L. Krieger, J. Org. Chem., 1976
,
41, 54; (b) T.
, 562; (c) J. D.
Nguyen, E. M. D’Amato, J. M. R. Narayanam, C. R. J. Stephenson,
Nature Chem. 2012 , 854; (d) H. Kim, C. Lee, Angew. Chem. Int.
Ed. 2012 51, 12303; (e) S. Y. Chow, M. Y. Stevens, L. Akerbladh,
S. Bergman, L. R. Odell, Chem. Eur. J. 2016 22, 9155; (f) C. K.
E6404.
Koike, M. Akita, Inorg. Chem. Front. 2014, 1
3
(a) J. C. Lo, D. Kim, C.-M. Pan, J. T. Edwards, Y. Yabe, J. Gui, T.
Qin, S. Gutierrez, J. Giacoboni, M. W. Smith, P. L. Holland, P.
S. Baran, J. Am. Chem. Soc. 2017, 139, 2484; (b) T. Qin, L. R.
Malins, J. T. Edwards, R. R. Merchant, A. J. E. Novak, J. Z.
Zhong, R. B. Mills, M. Yan, C. Yuan, M. D. Eastgate, P. S.
Baran, Angew. Chem. Int. Ed. 2017, 56, 260; (c) J. Streuff, A.
,
4
,
,
Prier, D. A. Rankic, D. W. C. MacMillan, Chem. Rev. 2013,
113, 5322.
Gansauer, Angew. Chem. Int. Ed. 2015, 54, 14232; (d) G. S. C. 13 (a) R. S. Herrick, T. R. Herrinton, H. W. Walker, T. L. Brown,
Srikanth, S. L. Castle, Tetrahedron 2005, 61, 10377; (e) P. D.
Curran, S. Hadida, S.-Y. Kim, Z. Luo, J. Am. Chem. Soc. 1999,
121, 6607.
For selected reviews, see: (a) J. K. Matsui, S. B. Lang, D. R.
Heitz, G. A. Molander, ACS Catal. 2017, 7, 2563; (b) C. K.
Prier, D. A. Rankic, D. W. C. MacMillan, Chem. Rev. 2013,
113, 5322; (c) J. W. Tucker, C. R. J. Stephenson, J. Org. Chem.
Organometallics 1985, 4, 42; (b) B. C. Gilbert, W. Kalz, C. I.
Lindsay, P. T. McGrail, A. F. Parsons, D. T. E. Whittaker, J.
Chem.Soc. Perkin Trans. 1 2000, 1187; (c) G. K. Friestad, J.
Qin, J. Am. Chem. Soc. 2001, 123, 9922; (d) G. K. Friestad, K.
Banerjee, Org. Lett. 2009, 11, 1095; (e) B. C. Gilbert, W. Kalz,
C. I. Lindsay, P. T. McGrail, A. F. Parsons, D. T. E. Whittaker,
Tetrahedron Lett. 1999, 40, 6095.
4
5
2012, 77, 1617; (d) K. L. Skubi, T. R. Blum, T. P. Yoon, Chem. 14 (a) Y. R. Luo, Comprehensive Handbook of Chemical Bond
Rev. 2016, 116, 10035; (e) S. Poplata, A. Trçster, Y.-Q. Zou, T.
Bach, Chem. Rev. 2016, 116, 9748; (f) N. A. Romero, D. A.
Nicewicz, Chem. Rev. 2016, 116, 10075.
(a) L. Chu, C. Ohta, Z. Zuo, D. W. C. MacMillan, J. Am. Chem.
Soc., 2014, 136, 10886; (b) A. Millet, Q. Lefebvre, M.
Rueping, Chem.–Eur. J., 2016, 22, 13464; (c) A. Gualandi, E.
Energies, CRC Press, Boca, Raton, 2007; (b) P. Nuhant, M. S.
Oderinde, J. Genovino, A. Juneau, Y. Gagne, C. Allais, G. M.
Chinigo, C. Choi, N. W. Sach, L. Bernier, Y. M. Fobian, M. W.
Bundesmann, B. Khunte, M. Frenette, O. O. Fadeyi, Angew.
Chem. Int. Ed. 2017, 56, 15309; (c) L. Wang, J. M. Lear, S. M.
Rafferty, S. C. Fosu, D. A. Nagib, Science 2018, 362, 225.
Matteucci, F. Monti, A. Baschieri, N. Armaroli, L. Sambri, P. 15 When the reaction is carried out under light for five minutes,
G. Cozzi, Chem. Sci., 2017, 8, 1613.
(a) T. Chinzei, K. Miyazawa, Y. Yasu, T. Koike, M. Akita, RSC
Adv. 2015, 5, 21297; (b) B. Tutkowski, E. Meggers, O. Wiest,
J. Am. Chem. Soc. 2017, 139, 8062; (c) D. R. Heitz, K. Rizwan, 16 (a) J. Liu, D. Obando, V. Liao, T. Lifaand, R. Codd, Eur. J. Med.
G. A. Molander, J. Org. Chem. 2016, 81, 7308.
(a) C. Nawrat, C. R. Jamison, Y. Slutskyy, D. W. C. MacMillan,
L. E. Overman, J. Am. Chem. Soc., 2015, 137, 11270; (b) G. L.
Lackner, K. W. Quasdorf, L. E. Overman, J. Am. Chem. Soc.,
2013, 135, 15342; (c) Y. Slutskyy, L. E. Overman, Org. Lett.,
2016, 18, 2564.
we can get a yield of 56%. When the reaction is carried out
under light for five minutes, and then to dark for 24 h, we
can get a yield of 80%.
6
7
Chem., 2011, 46, 1949; (b) G. Lamoureux, G. Artavia, Curr.
Med. Chem., 2010, 17, 2967.
8
A. ElMarrouni, C. B. Rittsb, J. Balsells, Chem. Sci. 2018, 9,
6639.
4 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C9CC06400A
Table of Contents (TOC)
Mn[0]
EWG
EWG
+
R I
Mn
R
sunlight
1o, 2o, 3o
inexpensive, abundant metal (Mn) catalyst
Visible-light-initiated Giese addition of unactivated alkyl iodides to electron-poor
olefins with catalysis by decacarbonyl dimanganese, Mn2(CO)10 was reported.