Page 5 of 7
Green Chemistry
Please do not adjust margins
Journal Name
COMMUNICATION
1
2
conformational specificity. To be specific, since the substrates
neutral to H-State and O-State were tolerated by both
photodecarbonylation and photocyclization, the addition of acid
could distinctly push the chemical equilibrium to the direction of
photocyclization, improving the yield of cyclization product (Scheme
4). As expected, after 10% PTSA was added, the 60% decarbonylation
product and trace cyclization product for 1p were turned to exclusive
cyclization product in 70% yield. Considering solitary evidence does
not stand, bromine (1ap), formonitrile (1aq) and methoxyl (1ar),
were introduced into the benzene ring of 1p. Similarly, all the three
substrates in the absence of acid produced decarbonylation products
in good yields and cyclization products in trace yields, while in the
presence of PTSA only afforded cyclization product in good yield.
Meanwhile, the experiments on some special substrates (Scheme 5)
suggested four aspects of structural conditions: (1) the hydrogen of
aldehyde group should be polar (1ba) and irreplaceable (1bb-1bd);
(2) the nitrogen of tertiary amine and the hydrogen of aldehyde
group should be close enough (1be-1bh); (3) the tertiary amine
cannot be replaced by secondary amines (1bi-1bj) which may form
hydrogen bond with aldehyde group; (4) the nitrogen of tertiary
amine cannot be replaced by carbon (1bk) or oxygen (1bl-1bn) which
have less ability to take hydrion. Clearly, the four aspects point in one
direction that the hydrogen of aldehyde group may be transferred to
the nitrogen of tertiary amine through the [1, 4]-H shift.
DOI: 10.1039/D0GC01256D
P. Malerich, T. J. Maimone, G. I. Elliott and D. Trauner, J. Am.
Chem. Soc., 2005, 127, 6276; (c) S. K. Murphy, J. W. Park, F. A.
Cruz and V. M. Dong, Science, 2015, 347, 56; (d) R. K.
Boeckman, J. Zhang and M. R. Reeder, Org. Lett., 2002, 4, 3891;
(e) W. Fan, S. Jiang and B. Feng, Tetrahedron, 2015, 71, 4035;
(f) M. C. Willis, Chem. Rev., 2010, 110, 725.
(a) M. A. Garralda, Dalton Trans., 2009, 19, 3635; (b) K. Sen and
J. C. Hackett, J. Am. Chem. Soc., 2010, 132, 10293; (c) T. Patra,
S. Manna and D. Maiti, Angew. Chem., Int. Ed., 2011, 50,
12140; (d) A. Modak, A. Deb, T. Patra, S. Rana, S. Maity and D.
Maiti, Chem. Commun., 2012, 48, 4253.
E. Taarning and R. Madsen, Chem. Eur. J., 2008, 14, 5638.
M. C. Brohmer, N. Volz and S. Brase, Synlett, 2009, 2009, 1383.
(a) T. Shibata, N. Toshida and K. Takagi, Org. Lett., 2002, 4,
1619; (b) T. Morimoto, K. Fuji, K. Tsutsumi and K. Kakiuchi, J.
Am. Chem. Soc., 2002, 124, 3806.
(a) A. Schirmer, M. A. Rude, X. Z. Li, E. Popova and S. B. del
Cardayre, Science, 2010, 329, 559; (b) N. Li, H. Norgaard, D. M.
Warui, S. J. Booker, C. Krebs and J. M. Bollinger, J. Am. Chem.
Soc., 2011, 133, 6158.
3
4
5
6
7
(a) T. Iwai, T. Fujihara and Y. Tsuji, Chem. Commun., 2008, 46,
6215; (b) T. Shibata, N. Toshida, M. Yamasaki, S. Maekawa and
K. Takagi, Tetrahedron, 2005, 61, 9974; (c) F. Y. Kwong, H. W.
Lee, W. H. Lam, L. Qiu and A. S. C. Chan, Tetrahedron:
Asymmetry, 2006, 17, 1238.
8
(a) P. Fristrup, M. Kreis, A. Palmelund, P. O. Norrby and R.
Madsen, J. Am. Chem. Soc., 2008, 130, 5206; (b) M. Kreis, A.
Palmelund, L. Bunch and R. Madsen, Adv. Synth. Catal., 2006,
348, 2148; (c) D. H. Doughty and L. H. Pignolet, J. Am. Chem.
Soc., 1978, 100, 7083; (d) J. Tsuji and K. Ohno, Tetrahedron
Lett., 1965, 6, 3969; (e) K. Ohno and J. Tsuji, J. Am. Chem. Soc.,
1968, 90, 99; (f) J. Tsuji and T. Ohno, Synthesis, 1969, 1, 157;
(g) H. Ho, K. Manna and A. D. Sadow, Angew. Chem., Int. Ed.,
2012, 51, 8607.
Conclusions
In summary, based on the “conformational-selectivity-based” design
strategy, we discovered a photodecarbonylation of aldehyde group
which proceeds efficiently under operationally simple and very mild
conditions. A wide variety of substrates are tolerated by this
photodecarbonylation, and this methodology is noteworthy in that it
does not require any catalysts. Furthermore, it also should be noted
that since our photodecarbonylation can be easily achieved by
introducing the tertiary amine into the ortho-position of aldehyde
group, whether we can design a special tertiary amine which does
not need to be introduced into the ortho-position of aldehyde group
but could directly realize the photodecarbonylation by means of
intermolecular reaction under mild conditions. Studies toward this
direction are ongoing in our laboratories.
9
(a) G. Domazetis, B. Tarpey, D. Dolphin and B. R. James, J.
Chem. Soc., Chem. Commun., 1980, 20, 939; (b) K. H. Park, S. U.
Son and Y. K. Chung, Chem. Commun., 2003, 75, 1898.
10 (a) S. Matsubara, Y. Yokota and K. Oshima, Org. Lett., 2004, 6,
2071; (b) D. Ferri, C.Mondelli, F. Krumeich and A. Baiker, J.
Phys. Chem. B, 2006, 110, 22982; (c) W. Li, C. Li, Y. Li, H. Tang,
H. Wang, Y. Pan and Y. Ding, Chem. Commun., 2018, 54, 8446;
(d) M. Chatterjee, T. Ishizakaa and H. Kawanami, Green Chem.,
2018, 20, 2345; (e) Akankshaa, D. Maiti, Green Chem., 2012,
14, 2314; (f) V. Ajdačić, A. Nikolić, M. Kerner, P. Wipf and I. M.
Opsenica, Synlett, 2018, 29, 1781.
Conflicts of interest
11 (a) T. Morioka, A. Nishizawa, T. Furukawa, M. Tobisu and N.
Chatani, J. Am. Chem. Soc., 2017, 139, 1416; (b) A. John, M. O.
Miranda, K. Ding, B. Dereli, M. A. Ortuño, A. M. LaPointe, G. W.
Coates, C. J. Cramer and W. B. Tolman, Organometallics, 2016,
35, 2391; (c) C. Jin, L. Gu and M. Yuan, Catal. Sci. Technol.,
2015, 5, 4341; (d) K. Ding, S. Xu, R. Alotaibi, K. Paudel, E. W.
Reinheimer and J. Weatherly, J. Org. Chem., 2017, 82, 4924.
12 (a) T. C. Fessard, S. P. Andrews, H. Motoyoshi and E. M.
Carreira, Angew. Chem., Int. Ed., 2007, 46, 9331; (b) H. W. Lee,
L. N. Lee, A. S. C. Chan and F. Y. Kwong, Eur. J. Org. Chem., 2008,
2008, 3403; (c) T. Morimoto, M. Fujioka, K. Fuji, K. Tsutsumi
and K. Kakiuchi, Pure Appl. Chem., 2008, 80, 1079.
There are no conflicts to declare.
Acknowledgements
This work was supported by the National Science Foundation of
China (21702236, 81803436 and 21772240), and the Doctor Initiated
Project
of
Guangdong
Natural
Science
Foundation
(2016A030310459). We thank the National Supercomputing Center
in Guangzhou for providing the computational resources. We also
thank Prof. Ruibo Wu at SYSU for his help in mechanism analysis.
13 (a) B. J. Morgan, C. A. Mulrooney and M.C. Kozlowski, J. Org.
Chem., 2010, 75, 44; (b) K. G. Liu, A. Chougnet and W. D.
Notes and references
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins