Communication
ChemComm
6
7
(a) M. Hatano, S. Suzuki and K. Ishihara, J. Am. Chem. Soc., 2006,
1
28, 9998; (b) M. Hatano, K. Yamashita, M. Mizuno, O. Ito and
K. Ishihara, Angew. Chem., Int. Ed., 2015, 54, 2707.
(a) S. L. Schreiber, Science, 2000, 287, 1964; (b) B. H. Rotstein,
S. Zaretsky, V. Rai and A. K. Yudin, Chem. Rev., 2014, 114,
8
1
323; (c) A. D ¨o mling, W. Wang and K. Wang, Chem. Rev., 2012,
12, 3083.
(a) N. A. Petasis and I. Akritopoulou, Tetrahedron Lett., 1993, 34, 583;
b) N. Kumagai, G. Muncipinto and S. L. Schreiber, Angew. Chem.,
Int. Ed., 2006, 45, 3635; (c) M. G. Ricardo, D. Llanes,
L. A. Wessjohann and D. G. Rivera, Angew. Chem., Int. Ed., 2019,
8, 2700.
(a) N. R. Candeias, F. Montalbano, P. M. S. D. Cal and P. M. P. Gois,
Chem. Rev., 2010, 110, 6169; (b) Y. Jiang, A. B. Diagne, R. J. Thomson
and S. E. Schaus, J. Am. Chem. Soc., 2017, 139, 1998; (c) Y. Jiang,
R. J. Thomson and S. E. Schaus, Angew. Chem., Int. Ed., 2017,
8
9
(
5
Scheme 2 Proposed mechanism.
5
6, 16631.
0 (a) J. M. R. Narayanam and C. R. J. Stephenson, Chem. Soc. Rev.,
011, 40, 102; (b) C. K. Prier, D. A. Rankic and D. W. C. MacMillan,
1
2
3
À1 20a
and the C(sp )–I bond of iodocyclohexane (60 kcal mol ).
Radical A then adds to iminium ion B (generated in situ by a
condensation reaction between 1a and 2a then protonated
by AcOH) to form radical cation C. Subsequent reduction of
C gives tertiary amine product 4 and makes a Hantzsch
Chem. Rev., 2013, 113, 5322; (c) N. A. Romero and D. A. Nicewicz,
Chem. Rev., 2016, 116, 10075; (d) Q.-Q. Zhou, Y.-Q. Zou, L.-Q. Lu and
W.-J. Xiao, Angew. Chem., Int. Ed., 2019, 58, 1586.
1 (a) N. R. Patel, C. B. Kelly, A. P. Siegenfeld and G. A. Molander,
ACS Catal., 2017, 7, 1766; (b) J. Jia, Q. Lefebvre and M. Rueping,
Org. Chem. Front., 2020, 7, 602; (c) P. Ji, Y. Zhang, Y. Wei, H. Huang,
W. Hu, P. A. Mariano and W. Wang, Org. Lett., 2019, 21, 3086;
1
+
21
ester to the radical cation, HE , which reacts with Mn(CO)
to regenerate the active catalyst [ Mn(CO) ] and terminate the
photocatalytic cycle.
In summary, we have developed a simple, scalable, and
modular three-component method for the synthesis of second-
5
I
(
d) H.-H. Zhang and S. Yu, J. Org. Chem., 2017, 82, 9995;
ꢀ
5
(e) D. P. Plasko, C. J. Jordan, B. E. Ciesa, M. A. Merrill and
J. M. Hanna, Photochem. Photobiol. Sci., 2018, 17, 534; ( f ) K. Cao,
S. M. Tan, R. Lee, S. Yang, H. Jia, X. Zhao, B. Qiao and Z. Jiang, J. Am.
Chem. Soc., 2019, 141, 5437; (g) Y. Li, K. Zhou, Z. Wen, S. Cao,
X. Shen, M. Lei and L. Gong, J. Am. Chem. Soc., 2018, 140, 15850.
ary amines with catalysis by Mn
2
(CO)10, an inexpensive 12 (a) J. Yi, S. O. Badir, R. Alam and G. A. Molander, Org. Lett., 2019,
2
1, 4853; (b) L. M. Kammer, M. Krumb, B. Spitzbarth, B. Lipp,
complex of an earth-abundant metal, under visible-light-
mediated conditions. This method employs readily accessible
J. K u¨ hlborn, J. Busold, O. M. Mulina, A. O. Terentev and T. Opatz,
Org. Lett., 2020, 22, 3318.
or commercially available materials to deliver an array of 13 (a) A. J. Fry and R. L. Krieger, J. Org. Chem., 1976, 41, 54; (b) T. Koike
and M. Akita, Inorg. Chem. Front., 2014, 1, 562; (c) J. D. Ngu-yen,
E. M. D. Amato, J. M. R. Narayanam and C. R. J. Stephenson,
Nat. Chem., 2012, 4, 854; (d) H. Kim and C. Lee, Angew. Chem., Int.
structurally and functionally diverse products, which would
otherwise be difficult to obtain in a single synthetic sequence
under such mild conditions. The method avoids traditional and
superstoichiometric radical initiators; the broad substrate
scope, excellent functional group tolerance, and mild condi-
tions suggest that it can be combined with other synthetic
methods to rapidly generate structural diversity.
Ed., 2012, 51, 12303.
4 W. P. Neumann, Synthesis, 1987, 665.
1
1
5 (a) C. Chatgilialoglu, C. Ferreri, Y. Landais and V. I. Timokhin,
Chem. Rev., 2018, 118, 6516; (b) R. Kumar, N. J. Flod ´e n,
W. G. Whitehurst and M. J. Gaunt, Nature, 2020, 581, 415.
6 T. Constantin, M. Zanini, A. Regni, N. S. Sheikh, F. Juli ´a and
D. Leonori, Science, 2020, 367, 1021.
7 (a) A. Hudson, M.-F. Lappert and B.-K. Nicholson, J. Chem. Soc.,
Dalton Trans., 1977, 551; (b) T. J. Meyer and J. V. Caspar, Chem. Rev.,
1
1
This work is supported by the National Natural Science
Foundation of China (21732002, 22077071). Dedicated to the
1
1
985, 85, 187; (c) B. Giese and J. Dupuis, Angew. Chem., Int. Ed. Engl.,
983, 22, 622; (d) B. Giese, Angew. Chem., Int. Ed. Engl., 1983, 22, 753;
100th anniversary of Chemistry at Nankai University.
(
e) B. Giese, J. A. Gonzalez-Gomez and T. Witzel, Angew. Chem., Int.
Ed. Engl., 1984, 23, 69.
Conflicts of interest
1
8 (a) R. S. Herrick, T. R. Herrinton, H. W. Walker and T. L. Brown,
Organometallics, 1985, 4, 42; (b) B. C. Gilbert, W. Kalz, C. I. Lindsay,
P. T. McGrail, A. F. Parsons and D. T. E. Whittaker, Tetrahedron Lett.,
There are no conflicts to declare.
1
999, 40, 6095; (c) B. C. Gilbert, W. Kalz, C. I. Lindsay, P. T. McGrail,
A. F. Parsons and D. T. E. Whittaker, J. Chem. Soc., Perkin Trans. 1,
000, 1187; (d) G. K. Friestad and J. Qin, J. Am. Chem. Soc., 2001,
123, 9922.
Discovery Today, 2017, 22, 965; (b) S. A. Lawrence, Amines: Synthesis 19 (a) H. Liang, Y.-X. Ji, R.-H. Wang, Z.-H. Zhang and B. Zhang, Org.
Notes and references
2
1
(a) J. Mayol-Llin `a s, A. Nelson, W. Farnaby and A. Ayscough, Drug
Properties and Applications, Cambridge University Press, Cambridge,
004; (c) A. Ricci, Amino Group Chemistry: From Synthesis to the Life
Sciences, Wiley-VCH, Weinheim, 2008; (d) E. Vitaku, D. T. Smith and
J. T. Njardarson, J. Med. Chem., 2014, 57, 10257.
Lett., 2019, 21, 2750; (b) W.-Z. Weng, H. Liang, R.-Z. Liu, Y.-X. Ji and
B. Zhang, Org. Lett., 2019, 21, 5586; (c) J.-Y. Dong, X.-C. Wang,
Z. Wang, H.-J. Song, Y.-X. Liu and Q.-M. Wang, Chem. Commun.,
2019, 55, 11707; (d) X.-C. Wang, J.-Y. Dong, Y.-Q. Li, Y.-X. Liu and
Q.-M. Wang, J. Org. Chem., 2020, 85, 7459.
2
2
3
P. Ruiz-Castillo and S. L. Buchwald, Chem. Rev., 2016, 116, 12564.
(a) M. Baumann, I. R. Baxendale, S. V. Ley and N. Nikbin, Beilstein 20 (a) Y. R. Luo, Comprehensive Handbook of Chemical Bond Energies,
J. Org. Chem., 2011, 7, 442; (b) M. Baumann and I. R. Baxendale,
Beilstein J. Org. Chem., 2013, 9, 2265.
A. F. Abdel-Magid and S. J. Mehrman, Org. Process Res. Dev., 2006,
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 and O. O. Fadeyi, Angew. Chem., Int. Ed.,
2017, 56, 15309; (c) L. Wang, J. M. Lear, S. M. Rafferty, S. C. Fosu and
D. A. Nagib, Science, 2018, 362, 225.
4
5
1
0, 971.
A. Olah, R. Krishnamurti and G. K. Surya, Comprehensive Organic
Synthesis, ed. B. M. Trost and I. Fleming, Pergamon Press. Oxford,
1
991, vol. 3, p. 293.
21 A. Trowbridge, D. Reich and M. J. Gaunt, Nature, 2018, 561, 522.
Chem. Commun.
This journal is © The Royal Society of Chemistry 2021