Visible-Light Promoted Distereodivergent Intramolecular Oxyamidation of Alkenes

Article abstract of DOI:10.1002/chem.201603977

The visible-light-promoted diastereodivergent intramolecular oxyamination of alkenes is described to construct oxazolindinones, pyrrolidinones and imidazolidones via mild generation of primary amidyl radicals from functionalized hydroxylamines. A unique phenomenon of highly diastereoselective ring-opening of aziridines controlled by electron sacrifices was observed. Highly diastereoselective amino alcohols derivatives were obtained efficiently through this protocol in gram scales. The mechanistic studies suggested the isolatable anti-aziridine intermediates were generated quickly from primary amidyl radicals and the diastereoselectivities were controlled by pK_avalues of the electron sacrifices.

Full text of DOI:10.1002/chem.201603977

A Journal of
Accepted Article
Title: Visible-Light Promoted Distereodivergent Intramolecular
Oxyamidation of Alkenes
Authors: Xiang Ren, Qihang Guo, Jianhui Chen, Hujun Xie, Qing Xu,
and Zhan Lu
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.201603977
Link to VoR: http://dx.doi.org/10.1002/chem.201603977
Supported by

10.1002/chem.201603977
Chemistry - A European Journal
COMMUNICATION
Visible-Light Promoted Distereodivergent Intramolecular
Oxyamidation of Alkenes
Xiang Ren, [a]† Qihang Guo, [a]† Jianhui Chen, [a,c] Hujun Xie, *[b] Qing Xu* [c] and Zhan Lu*[a]
Dedication ((optional))
rhodium-catalyzed intermolecular oxyamination of indoles by
using different oxygen nucleophiles.[3j] However, the substrates
were limited in indoles. Xu and co-workers reported
a
diastereoselectively iron-catalyzed intramolecular oxyamination
of olefins controlled by careful selection of counteranion/ligand
combinations.[3w] However, in both cases, there were only one
reversed example shown via amidyl-carbenes or amidyl-metal
intermediates, and no direct evidences to explain the
controllable selectivity.
Visible light is a safe, inexpensive, abundant, and nonpolluting
reagent, [10] meanwhile, could promote to generate amidyl radical
mildly.[11] Very recently, Akita[12] and Leonori[13], respectively,
reported the oxyamination of alkenes via visible light
photocatalysis. However, the reactions of 1,2-disubstituted
alkenes afforded products with poor diastereoselectivities. To
the best of our knowledge, the use of photosensitizer to promote
the diastereoselectivity-controllable oxyamination reaction of the
same alkene has not previously been described.[14] Our group
are particularly interested in one-electron reduction of nitrogen-
containing electron-deficient groups.[15] Here, we described a
Abstract:
The
visible-light-promoted
diastereodivergent
intramolecular oxyamination of alkenes and amination of unactivated
C(Sp3)-H bonds is described to construct oxazolindinones,
pyrrolidinones and imidazolidones via mild generation of primary
amidyl radicals from functionalized hydroxylamines.
A unique
phenomenon on highly diastereoselective ring-opening of aziridines
controlled by electron sacrifices was observed. High diastereoselective
amino alcohols derivatives were obtained efficiently through this
protocol in gram scales. The mechanistic studies suggested the
isolatable anti-aziridine intermediates were generated quickly from
primary amidyl radicals and the diastereoselectivities were controlled
by pKa values of electron sacrifices.
1,2-Amino alcohols derivatives are highly-value, widely exist
and well used in organic transformation for asymmetric catalysts,
medicine, materials and so on. The directly and highly regio- and
diastereoselective oxyamination of alkenes is one of the
powerful methodologies to construct useful amino alcohols
derivatives.[1] Since Bäckvall reported the first direct
oxyaminations of alkenes using stoichiometric PdCl2 in 1975[2]
and Sharpless reported the first example of Os-catalyzed
oxyamination of alkenes,[3] direct oxyamination of alkenes were
developed to explore their utilities. Although highly chemo- and
regioselective oxyamidations of alkenes were achieved through
transition-metal catalysis, [4] hypervalent iodine,[5] acids,[6] NFSI,[7]
as well as electrochemistry[8], distereoselectivity-controllable
oxyamidation reaction of alkenes, particularly based on radical-
initiated reactions, is a remaining significant challenge. The
diastereoselectivity-controllable oxyamination of alkenes used to
be controlled by using Z or E-configuration alkenes.[9] Dauban
and co-workers developed a diastereoselectivity-controllable
mechanistic
distinct
diastereroselectivity-controllable
intramolecular oxyamidation of alkenes with functionalized
hydroxylamines in the presence of photocatalysts and electron-
sacrifices upon irradiation of visible light.
[a]
[b]
[c]
Mr. X. Ren, Mr. Q. Guo, Mr. J. Chen, Prof. Z. Lu
Department of Chemistry, Zhejiang University
Hangzhou, Zhejiang 310058, P. R. China
E-mail: luzhan@zju.edu.cn
Scheme 1. Regio- and stereoselective oxyamination of alkenes.
Prof. H. Xie
Department of Applied Chemistry, Zhejiang Gongshang University,
Hangzhou, Zhejiang 310018, P. R. China
E-mail: hujunxie@gmail.com
We chose 1a as a model substrate. The transformation of 1a
using transition metal catalysts has been studied to form
aziridine or oxyamidation products.[4n,9c] In particular, the
reaction of 1a gave the oxyamidation products in good yield with
poor diastereoselectivity using iron catalysts.[3w] On the contrary,
we proposed that the primary amidyl radical might be formed
through the one-electron reductive process.[16] The reaction of
1a was conducted in the presence of 2 mol% of visible light
J. Chen, Prof. Q. Xu
College of Chemistry and Materials Engineering, Wenzhou
University, Wenzhou 325035, P. R. China
E-mail: qing-xu@wzu.edu.cn
† X. Ren and Q. Guo are contributed equally to this work
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/chem.201603977
Chemistry - A European Journal
COMMUNICATION
Table 1. Optimization.[a]
PhNMe2 (pKa value is 5.2, entry 10) and N-Me-morpholine (pKa
value is 7.38, entry 11) were selected as electron sacrificial
donors to give the oxyamidation products with 1:6 and 1.4:1 dr,
respectively. The reactions could be accelerated at 50 oC
(entries12 and 13, as the two standard conditions). Using 10
mol% of Et3N, the reaction gave the oxyamidation products with
1:1.3 dr (entery 14). The reversed diastereoselectivity was
observed using 1 mol% of Et3N (entery 15). This unique
diastereoselectivity-controllable reactions were dependent on
pKa value of electron sacrificial donors and pH value of
Additives
(equiv)
Yield
[b](%)
Dr
Entry
Photocatalyst
[b]anti/syn
Ir(ppy)2(dtbbpy)PF6
-
Et3N (1)
Et3N (1)
-
65
0
>20:1
-
1
2
reactions.
The
organic
photosensitizers
such
as
Tetrabromofluorescein and Rose Bengal could promote the
same transiformations with slightly poor reactivities and
diastereoselectivities (entries 16-19).
Ir(ppy)2(dtbbpy)PF6
Ir(ppy)2(dtbbpy)PF6
Ir(ppy)2(dtbbpy)PF6
Ir(ppy)2(dtbbpy)PF6
Ir(ppy)2(dtbbpy)PF6
Ir(ppy)2(dtbbpy)PF6
Ir(ppy)2(dtbbpy)PF6
Ir(ppy)2(dtbbpy)PF6
Ir(ppy)2(dtbbpy)PF6
Ir(ppy)2(dtbbpy)PF6
Ir(ppy)2(dtbbpy)PF6
Ir(ppy)2(dtbbpy)PF6
Ir(ppy)2(dtbbpy)PF6
Tetrabromofluorescein
Tetrabromofluorescein
Rose bengal
0
-
3
4[c]
5
Et3N (1)
PPh3 (1)
PhSiH3 (1)
Et3SiH (1)
(EtO)3SiH (1)
Ph3N (1)
PhNMe2 (1)
0
-
With standard conditions in hand, we investigated the scope
of substrates shown in Table 2. Using electron-deficient benzoyl
group, the diastereoselectivities were improved dramatically
under both Et3N and Ph3N conditions (2b-d and 3b-d). The
reactions with ortho- and meta-methylphenyl alkenes gave anti-
selective products 2e-f with high diastereoselectivity under Et3N
conditions, and syn-selective products 3e-f with a slightly low
diastereoselectivity under Ph3N conditions. Simple phenyl ring
1g, and phenyl ring with electron-donating groups 1h, phenyl
group 1i and electron-withdrawing groups 1j could participate to
60
0
4:1
-
6
0
-
7
21
50
68
68
(69)[e]
(74)[e]
72
90
69
67
70
72
1:3
1:10
1:6
1.4:1
>20:1
1:12
1:1.3
1:5
13:1
1:12
13:1
1:5
8
9
10
11
12[d]
13[d]
14[d]
15[d]
16[d]
17[d]
18[d]
19[d]
N-Me-morpholine
(1)
give
the
anti-selective
products
2g-j
with
high
diastereoselectivity under Et3N conditions, and syn-selective
products 3g-k with a slightly low diastereoselectivity. Both 1-
naphthyl and 2-naphthyl alkenes could be transferred to the
desired anti- and syn-products with high diastereoselectivities
(2l-m and 3l-m). Heterocycles such as 2-(N-tosyl)indolyl could
be tolerated to afford the desired anti-2m in 52% yield with >20/1
dr. The syn-3m could also be obtained under Ph3N conditions in
76% yield with >20/1 dr. The alkyl alkene 1n could undergo
Et3N (1)
Ph3N (1)
Et3N (0.1)
Et3N (0.01)
Et3N (1)
oxyamidation reactions
to afford the same major
Ph3N (1)
Et3N (1)
diastereoisomer under both conditions. Dimethyl alkenes and
terminal alkenes afforded the oxyamidation product in 59% and
41% yield, respectively. The carbon-tethered substrate 4 could
also participate to afford the pyrrolidinone 5 in 57% with 14/1 dr
and 52% yield with 7/1 dr under conditions A and B, respectively.
The configurations of major products were somehow the same.
The nitrogen-tethered substrate 6 was converted to aziridine 7[18]
in 66% yield under conditions A. The oxyamination product 8
was produced in 49% yield with 6/1 dr under conditions B.
Notably, the reaction of 6 under conditions B with an excess
Rose bengal
Ph3N (1)
[a] The reaction was conducted using 2 mol% of photocatalyst, 1 equiv. of
additive and 0.5 mol of substrate in a solution of MeCN (0.05 M) under the
irradiation of blue LED (5 W). [b] Yields and diastereoselectivities were
determined by H NMR using crude products and the trimethylsilylbenzene as
an internal standard. [c] No light. [d] 50 oC. [e] In 1 hour, and isolated yields of
the major isomer in the parenthesis.
o
equivalent of benzoic acid at 80 C afforded the imidazolidone 8
photocatalyst Ir(ppy)2(dtbbpy)(PF6) and 1 equiv. of Et3N (pKa
value is 10.75)[17] as an electron sacrificial donor in a solution of
MaCN (0.05M) under the irradiation of 5 W of blue LED at room
temperature to afford the oxyamidation product anti-2a, in 65%
yield with >20:1 distereoselectivity (Table 1, entry 1). Control
experiments suggested that photocatalysts, light, bases are all
necessary (entries 2-4). Various e-sacrificial donors have been
in 62% yield with >20/1 dr. The relative configurations of
oxyamination
products
were
determined
by
X-ray
crystallographic analysis of compounds 2e, 3e and 8. [19]
The gram-scale reaction could be conducted smoothly to afford
the anti- and syn-products in 77% and 93% isolated yield,
respectively (Scheme 2). The amino alcohols could be obtained
by hydrolysis of the oxyamidation products.
investigated. Triphenylphosphine is also
a good electron
sacrificial donor to afford the desired anti-product in 60% yield
and 4:1 dr (entry 5). Silanes could not efficiently promote the
process at room temperature, and diastereoselectivities was
less ideal (entires 6-8). To our surprise, the reactions using Ph3N
(pKa value is -3.04, entry 9) as the electron sacrificial donor
afforded syn-product 3a as the major products with 1/10 dr.
Scheme 2. Gram scale reactions.
This article is protected by copyright. All rights reserved.

10.1002/chem.201603977
Chemistry - A European Journal
COMMUNICATION
Table 2. Substrate scope for diastereoselectivity-controllable oxyamidation of alkenes
[a] Conditions: Ir(ppy)2(dtbbpy)PF6 (2 mol%), base (1 equiv.), 1 (0.5 mol), and MeCN (0.05 M), blue LED (5 W), 50 oC. [b] 80 oC, with 1 equiv. of PhCOOH.
To elucidate the mechanism, a series of experiments were
conducted. 1) The reaction did not occur in the presence of
radical inhibitor tempo (Scheme 3). This suggested the reaction
might undergo a radical initiated pathway.[20] 2) Time course
studies were conducted to show that the reactions of 1a in the
Scheme 3. Radical trapped reactions.
presence of Et3N or Ph3N afforded the same aziridine
intermediate 9a which could be observed by analysis of crude
1
mixtures, also isolated and identified by H and 13C NMR, NOE
and HRMS. The control experiments were carried out under the
irradiation by visible light in 15 min, then the mixtures were
stirred in dark in 18 h to afford anti-2a or syn-3a, respectively
(Scheme 4). In the presence of Et3N or Ph3N with benzolic acid,
9a could also be translated to the corresponding anti-2a in 61%
yield and 16/1 dr or syn-3a in 74% yield and 10/1 dr,
respectively (Scheme 4). These results suggested: one is that
the aziridine might be the stable intermediate during the reaction
pathways, another is that the controllable diastereoselectivity of
the products should be somehow involved by the ring-open step
of the aziridine intermediate.[21] 3) The reactions of Z-1a in the
Scheme 4. Time course studies and reactions of intermediates.
presence of Et3N or Ph3N afforded the anti-2a in 67% yield with
8/1 dr or syn-3a in 55% yield with 11/1 dr, respectively. These
results were similar with ones using E-1a as the substrate. It
would be unlikely to generate the nitrene intermediates which
would react with alkenes with different configurations to afford
stereo-specific products.[22] The nitrogen radical intermediates
seemed more reasonable. The nitrene intermediates could not
be absolutely ruled out from primary amidyl radicals.
Scheme 5. Reactions of Z-1a.
This article is protected by copyright. All rights reserved.

10.1002/chem.201603977
Chemistry - A European Journal
COMMUNICATION
In order to elucidate the origin of the observed stereoselectivity,
we carried out the density functional theory (DFT) calculations to
investigate the reaction mechanisms for the nucleophilic attack
step by the benzolic anion for the formation of products.[23] The
corresponding Gibbs free energy profiles for this step in the
presence of Ph3N (I) and Et3N (II) are illustrated in Figure 1. As
shown in Figure 2(I), the Ph3N is not involved in the nucleophilic
attack step due to the smaller proton affinity of Ph3N (218.8
kcal/mol) compared to Et3N (232.0 kcal/mol). This reaction can
proceed via two possible pathways. The barrier difference (4.5
kcal/mol, between TS12 and TS13) for the formation of the two
diastereoisomers can give a multiplicative difference of about
103 in the reaction rate if we assume an Arrhenius expression for
the rate constant and similar preexponential factors, explaining
the experimental observations that the reaction could afford syn-
3 as the major product in the presence of Ph3N. For the Et3N,
the barrier difference (3.1 kcal/mol, between TS45 and TS46) for
aziridine and benzoic acid pair B might form a intermolecular D,
then a SN1-reaction pathway might proceed to give syn-3
products.[24] This interesting phenomenon to control the
diastereoselectivity will potentially provide a novel strategy for
diastereoselective ring-opening of aziridines.
the formation of the two diastereoisomers can give
a
multiplicative difference of about 102 in the reaction rate. The
calculation results agree with the experimentally observed
selectivity that the reaction could afford anti-2 as the major
product in the presence of Et3N.
Scheme 6. Possible Mechanism.
In summary, we developed
a first visible-light-promoted
diastereodivergent intramolecular oxyamidation of alkenes with
functionalized hydroxylamines. The unique diastereodivergent
reactions were controlled by pKa value of electron sacrificial
donors and pH value of reactions. This protocol afforded useful
amino alcohols derivatives with high diastereoselectivities in
gram scales. The mechanistic studies suggested that primary
amidyl radicals were mildly generated from functionalized
hydroxylamines in the presence of photocatalysts and amines
upon irradiation of visible light, aziridine intermediates were
formed quickly and the high diastereoselectivities were
dependent on ring-opening of aziridine intermediates. Visible-
light-promoted selectivity-controllable intermolecular reactions
and asymmetric transformations will be explored in our
laboratory.
Figure 1. Free energy profiles of the nucleophilic attack step by benzoyl group
for the formation of different products in the presence of Ph3N (I) and Et3N (II).
The solvation-corrected relative Gibbs free energies are given in kcal/mol.
Acknowledgements
The possible mechanism was shown in Scheme 6. The visible
light photocatalyst (PC) could absorb the visible light to generate
the excited state PC* which could be reduced by electron
sacrifices to produce the low valent photocatalyst PC-. The
substrate could be reduced by PC species to regenerate PC and
afford the radical ion intermediate which might undergo O-N
bond cleavage to form a distonic radical ion A. The primary
amidyl radical could undergo the intramolecular radical
cyclization to afford a benzylic radical which might lose an
electron to form a stable aziridine intermediate[21] with the
benzoic acid. Although the possibility of the nitrene obtained
through deprotonation of A is small, we can not absolutely
exclude this pathway. In the presence of Et3N, the benzoic acid
could react with Et3N to form +NHEt3 and benzoic ion which
might be favor to attack the aziridine intermediate undergo SN2-
reaction pathway to give anti-2. Due to the weak acidic property,
Ph3N could not react with the benzoic acid efficiently. The
We thank the NSFC (21472162).
Keywords: visible light photocatalysis • diastereodivergent •
oxyamidation • aziridines • alkenes
[1]
T. J. Donohoe, C. K. A. Callens, A. Flores, A. R. Lacy, A. H. Rathi,
Chem. Eur. J. 2011, 17, 58.
[2]
[3]
J. E. Bäckvall, Tetrahedron Lett. 1975, 16, 2225.
a) K. B. Sharpless, A. O. Chong, K. Oshima, J. Org. Chem. 1976, 41,
177; b) G. Li, H.-T. Chang, K. B. Sharpless, Angew. Chem. Int. Ed.
1996, 35, 451.
[4]
For selected examples on transition-metal catalyzed oxyamination of
alkenes, see: [Pd]: a) E. J. Alexanian, C. Lee, E. J. Sorensen, J. Am.
Chem. Soc. 2005, 127, 7690; b) P. Szolcsanyi, T. Gracza, Chem.
Commun. 2005, 3948; c) G. Liu, S. S. Stahl, J. Am. Chem. Soc. 2006,
128, 7179; d) L. V. Desai, M. S. Sanford, Angew. Chem. Int. Ed. 2007,
46, 5737; e) H. Zhu, P. Chen, G. Liu, J. Am. Chem. Soc. 2014, 136,
This article is protected by copyright. All rights reserved.

10.1002/chem.201603977
Chemistry - A European Journal
COMMUNICATION
1766. [Pt]: f) K. Muniz, A. Iglesias, Y. Fang, Chem. Commun. 2009,
5591. [Rh]: g) A. Padwa, T. Stengel, Org. Lett. 2002, 4, 2137; h) E.
Levites-Agababa, E. Menhaji, L. N. Perlson, C. M. Rojas, Org. Lett.
2002, 4, 863; i) S. Beaumont, V. Pons, P. Retailleau, R. H. Dodd, P.
Dauban, Angew. Chem. Int. Ed. 2010, 49, 1634; j) G. Dequirez, J.
Ciesielski, P. Retailleau, P. Dauban, Chem. Eur. J. 2014, 20, 8929;
[Au]: k) T. de Haro, Nevado, C. Angew. Chem. Int. Ed. 2011, 50, 906;
[Os]: l) J. Streuff, B. Osterath, M. Nieger, K. Muñiz, Tetrahedron:
Asymmetry 2005, 16, 3492; and ref.9; [Cu]: m) M. Noack, R. Gottlich,
Chem. Commun. 2002, 536. n) R. Liu, S. R. Herron, S. A. Fleming, J.
Org. Chem. 2007, 72, 5587; o) D. J. Michaelis, C. J. Shaffer, T. P. Yoon,
J. Am. Chem. Soc. 2007, 129, 1866; p) D. J. Michaelis, M. A. Ischay, T.
P. Yoon, J. Am. Chem. Soc. 2008, 130, 6610; q) T. Benkvoics, I. A.
Guzei, T. P. Yoon, Angew. Chem. Int. Ed. 2010, 49, 9153; r) P. H.
Fuller, J. W. Kim, S. R. Chemler, J. Am. Chem. Soc. 2008, 130, 17638;
s) M. C. Paderes, S. R. Chemler, Org. Lett. 2009, 11, 1915; [Fe]: t) K. S.
Williamson, T. P. Yoon, J. Am. Chem. Soc. 2010, 132, 4570; u) K. S.
Williamson, T. P. Yoon, J. Am. Chem. Soc. 2012, 134, 12370; v) T.
Kamon,; D. Shigeoka, T. Tanaka, T. Yoshimitsu, Org. Biomol. Chem.
2012, 10, 2363; w) G.-S.Liu, Y.-Q. Zhang, Y.-A. Yuan, H. Xu, J. Am.
Chem. Soc. 2013, 135, 3343; x) D.-F. Lu, C.-L. Zhu, Z.-X. Jia, H. Xu, J.
Am. Chem. Soc. 2014, 136, 13186; y) L. Legnani, B. Morandi, Angew.
Chem. Int. Ed. 2016, 55, 2248.
Weinheim, 2001; Vol. 2, pp 407-424; f) S. Z. Zard, Chem. Soc. Rev.
2008, 37, 1603. For selected examples on primary amidyl radicals, see:
g) M. Newcomb, M. T. Burchill, J. Am. Chem. Soc. 1988, 110, 6528; h)
Y. Guindon, B. Guérin, S. R. Landry, Org. Lett. 2001, 3, 2293; i) Y.
Tang, C. Li, Org. Lett. 2004, 6, 3229; j) P. Gaudreault, C. Drouin, J.
Lessard, Can. J. Chem. 2005, 83, 543; k) J. Kemper, A. Studer, Angew.
Chem. Int. Ed. 2005, 44, 4914; l) A. Martin, I. Pérez-Martín, E. Suárez,
Org. Lett. 2005, 7, 2027. m) T. Hu, M. Shen, Q. Chen, C. Li, Org. Lett.
2006, 8, 2647; n) J. Guin, C. Mück-Lichtenfeld, S. Grimme, A. Studer, J.
Am. Chem. Soc. 2007, 129, 4498.
[12] K. Miyazawa, T. Koike, M. Akita, Chem. Eur. J. 2015, 21, 11677.
[13] J. Davies, S. G. Booth, S. Essafi, R. A. W. Dryfe, D. Leonori, Angew.
Chem. Int. Ed. 2015, 54, 14017.
[14] During revising this manuscript,
a photocatalytic oxyamination of
alkenes was reported by Xiao group, see: X.-Q. Hu, J. Chen, J.-R.
Chen, D.-M. Yan, W.-J. Xiao, Chem. Eur. J. 2016, 22, 14141.
[15] C. Wang, X. Ren, H. Xie, Z. Lu, Chem. Eur. J. 2015, 21, 9676.
[16] a) K. Okada, K. Okamoto, N. Morita, K. Okubo, M. Oda, J. Am. Chem.
Soc. 1991, 113, 9401; b) M. J. Schnermann, L. E. Overman, Angew.
Chem. Int. Ed. 2012, 51, 9576; c) G. Cecere, C. M. Konig, J. L. Alleva,
D. W. C. MacMillan, J. Am. Chem. Soc. 2013, 135, 11521; d) D.
Kalyani, K. B. McMurtrey, S. R. Neufeldt, M. S. Sanford, J. Am. Chem.
Soc. 2014, 136, 5607; e) Q. Qin, S. Yu, Org. Lett. 2014, 16, 3504.
[17] All of the pKa data from Evan’s pKa table.
[5]
[6]
a) K. C. Nicolau, P. S. Baran, Y. L. Zhong, S. Barluenga, K. W. Hunt, R.
Kranich, J. A. Vega, J. Am. Chem. Soc. 2002, 124, 2233; b) B. M.
Cochran, F. E. Michael, Org. Lett. 2008, 10, 5039; c) D. J. Wardrop,
E. G. Bowen, R. E. Forslund, A. D. Sussman, S. L. Weerasekera,
J. Am. Chem. Soc. 2010, 132, 1188; d) Q. Xue, J. Xie, P. Xu, K.
Hu, Y. Cheng, C. Zhu, ACS Catalysis 2013, 3, 1365.
[18] For examples on visible-light-promoted aziridinations of olefins, see: a)
S. O. Scholz, E. P. Farney, S. Kim, D. M. Bates, T. P. Yoon, Angew.
Chem. Int. Ed. 2016, 55, 2239; b) K. Matsuzawa, Y. Nagasawa, E.
Yamaguchi, N. Tada, A. Itoh, Synthesis 2016, DOI:10.1055/s-0035-
1561635. During revising this manuscript,
a
cobalt-catalyzed
a) J. M. Mahoney, C. R. Smith, J. N. Johnston, J. Am. Chem. Soc.
2005, 127, 1354; b) V. A. Schmidt, E. J. Alexanian, J. Am. Chem. Soc.
2011, 133, 11402; c) K. Moriyama, Y. Izumisawa, H. Togo, J. Org.
Chem. 2012, 77, 9846.
aziridination of alkenes was reported by Zhang group, see: H. Jiang, K.
Lang, H. Lu, L. Wojtas, X. P. Zhang, Angew. Chem. Int. Ed. 2016, 55,
11604.
[19] CCDC 1443389, 1443391 and 1496350.
[7]
[8]
Y. Li, M. Hartmann, C. G. Daniliuc, A. Studer, Chem. Commun. 2015,
51, 5706.
[20] The energy transfer mechanism could not be absolutely ruled out. For
selected examples, see: a) Z. Lu, T. P. Yoon, Angew. Chem. Int. Ed.
2012, 51, 10329; b) E. P. Farney, T. P. Yoon, Angew. Chem. Int. Ed.
2014, 53, 793; c) R. Alonso, T. Bach, Angew. Chem. Int. Ed. 2014, 53,
4368; d) E. Arceo, E. Montroni, P. Melchiorre, Angew. Chem. Int. Ed.
2014, 53, 12064.
a) H.-C. Xu, K. D. Moeller, J. Am. Chem. Soc. 2008, 130, 13542; b) H.-
C. Xu, K. D. Moeller, J. Am. Chem. Soc. 2010, 132, 2839; c) F. Xu, L.
Zhu, S. Zhu, X. Yan, H.-C. Xu, Chem. Eur. J. 2014, 20, 12740.
a) T. J. Donohoe, P. D. Johnson, M. Helliwell, M. Keenan,
Chem.Commun. 2001, 2078; (b) T. J. Donohoe, G. H. Churchill, K. M.
P. Wheelhouse, P. A. Glossop, Angew. Chem. Int. Ed. 2006, 45, 8025;
b) T. J. Donohoe, M. J. Chughtai, D. J. Klauber, D. Griffin, A. D.
Campbell, J. Am. Chem. Soc. 2006, 128, 2514; c) T. J. Donohoe, C. J.
R. Bataille, W. Gatrell, J. Kloesges, E.Rossignol, Org. Lett. 2007, 9,
1725; d) T. J. Donohoe, A. Flores, C. J. R. Bataille, F. Churruca, F.
Angew. Chem. Int. Ed. 2009, 48, 6507; e) T. J. Donohoe, P. J. Lindsay-
Sott, J. S. Parker, Tetrahedron Lett. 2009, 50, 3523.
[9]
[21] For a acidity and polarity controlled divergent aziridine opening process,
see: a) Berti, C.; Camici, G.; Macchia, B.; Macchia, F.; Monti, L.
Tetrahedron Lett 1972, 25, 2591; for a regiodivergent aziridine opening
under Schiff base catalysis, see: b) Xu, Y.; Kaneko, K.; Kanai, M.;
Shibasaki, M.; Matsunaga, S. J. Am. Chem. Soc. 2014, 136, 9190; for a
two-step examples on the stereodivergent synthesis of vic-amino
alcohols from aziridines, see: c) B. Olofsson, U. Khamrai, P. Somfai,
Org. Lett. 2000, 2, 4087; d) B. Olofsson, P. Somfai, J. Org. Chem. 2002,
67, 8574.
[10] a) C. K. Prier, D. A. Rankic, D. W. C. MacMillan, Chem. Rev. 2013, 113,
5322; For a review on visible-light-promoted reactions of nitrogen-
radicals, see: b) J.-R. Chen, X.-Q. Hu, L.-Q. Lu, W.-J. Xiao, Chem. Soc.
Rev. 2016, doi: 10.1039/c5cs00655d. For a review on visible-light-
promoted olefin difunctionalizations, see: c) M. Cao, X. Ren, Z. Lu,
Tetrahedron Lett., 2015, 56, 3732.
[22] For selected reviews on nitrenes and aziridines, see: a) I. D. G. Watson,
L. Yu, A. K. Yudin, Acc. Chem. Res. 2006, 39, 194; b) G. S. Singh, M.
D’hooghe, N. De Kimpe, Chem. Rev. 2007, 107, 2080; c) H. Ohno,
Chem. Rev. 2014, 114, 7784; d) L. Degennaro, P. Trinchera, R. Luisi,
Chem. Rev. 2014, 114, 7881.
[11] For selected reviews on amidyl radicals, see: a) L. Stella, Angew.
Chem. Int. Ed. 1983, 22, 337; b) J. L. Esker, M. Newcomb, In Advances
in Heterocyclic Chemistry; A. R. Katritzky, Ed.; Academic Press: New
York, 1993; Vol. 58, pp1-45; c) S. Z. Zard, synlett 1996, 1148; d) A. G.
Fallis, I. M. Brinza, Tetrahedron 1997, 53, 17543; e) L. Stella, In
Radicals in Organic Synthesis; P. Renaud, M. P. Sibi, Eds.; Wiley-VCH:
[23] The computational details can be found in supporting information.
[24]
D. Ferraris, W. J. Drury III, C. Cox , T. Lectka, J. Org. Chem. 1998, 63,
4568.
This article is protected by copyright. All rights reserved.

10.1002/chem.201603977
Chemistry - A European Journal
COMMUNICATION
Entry for the Table of Contents (Please choose one layout)
Layout 2:
COMMUNICATION
Author(s), Corresponding Author(s)*
Page No. – Page No.
Visible-Light Promoted
Distereodivergent Intramolecular
Oxyamidation of Alkenes
The visible-light-promoted diastereodivergent intramolecular oxyamination of alkenes
and amination of unactivated C(Sp3)-H bonds is described to construct oxazolindinones,
pyrrolidinones and imidazolidones via mild generation of primary amidyl radicals from
functionalized hydroxylamines. A unique phenomenon on highly diastereoselective ring-
opening of aziridines controlled by electron sacrifices was observed. High
diastereoselective amino alcohols derivatives were obtained efficiently through this
protocol in gram scales. The mechanistic studies suggested the isolatable anti-aziridine
intermediates were generated quickly from amidyl radicals and the diastereoselectivity
were controlled by pKa values of electron sacrifices.
This article is protected by copyright. All rights reserved.