10.1002/chem.202003840
Chemistry - A European Journal
FULL PAPER
Standard procedure for synthesis of 3-phenyl-2-tosyl-2,3-dihydro-
A. D. Lackner, H. P. Shunatona, E. Tkatchouk, W. A. Goddard III and F.
D. Toste, Angew. Chem., Int. Ed., 2010, 49, 5519–5522; (k) T. Wang, S.
Shi, P. Daniel, E. Rettenmeier, M. Rudolph, F. Rominger, A. S. K.
Hashmi. Chem. Eur. J. 2014, 20, 292–296; (l) A. S. K. Hashmi, T.
Wang, S. Shi, M. Rudolph. J. Org. Chem. 2012, 77, 7761−7767; (m) A.
S. Hashmi, M. Bührle, R. Salathé, J. Bats, Adv. Synth. Catal. 2008, 350,
2059–2064; (n) A. S. K. Hashmi, T. M. Frost and J. W. Bats, J. Am.
Chem. Soc., 2000, 122, 11553–11554; (o) A. S. K. Hashmi, M. C.
Blanco, D. Fischer and J. W. Bats, Eur. J. Org. Chem. 2006, 1387–
1389; (p) H. Jin, B. Tian, X. Song, J. Xie, M. Rudolph, F. Rominger, A.
S. K. Hashmi, Angew. Chem., Int. Ed., 2016, 55, 12688–12692; q) Y.
Zheng, J. Zhang, X. Cheng, X. Xu, L. Zhang, Angew. Chem. Int. Ed.
2019, 58, 5241–5245; r) C. Shu, C.-Y.Shi, Q. Sun, B. Zhou, T. -Y.Li, Q.
He, X. Lu, R.-S. Liu, L.-W. Ye, ACS Catal. 2019, 9,1019 –1025. s) J.-M.
Yang, Y.-T. Zhao, Z.-Q. Li, X.-S. Gu, S.-F. Zhu, Q.-L. Zhou, ACS Catal.
2018, 8, 7351–7355.
1H-imidazo[1,5-a]indole
(5a)
and
(S)-2-((R)-
phenyl(phenylamino)methyl)-1-tosylazetidin-3-one (6a).
A Schlenk tube was charged with P(t-Bu)2(o-biphenyl)AuCl (0.0053 g,
0.01 mmol) and AgSbF6 (0.0034g, 0.01 mmol), and to this mixture was
added dry DCM (2 mL). The resulting mixture was stirred at room
temperature for 5 min, and to this mixture was added a dry DCM solution
(3 mL) of 4-methyl-N-(prop-2-yn-1-yl)benzenesulfonamide 1a’ (0.041 g,
0.2 mmol) and (Z)-N-benzylideneaniline oxide 2a (0.0473 g, 0.24 mmol)
dropwise. After stirring at room temperature for 30 h, the reaction mixture
was filtered over a short celite bed and concentrated to crude products
5a and 6a. Flash column chromatography on a silica column (ethyl
acetate/hexane = 1:20) afforded the desired 3-phenyl-2-tosyl-2,3-dihydro-
1H-imidazo[1,5-a]indole 5a (0.048 g, 0.12 mmol, 63%) as white solid and
(S)-2-((R)-phenyl(phenylamino)methyl)-1-tosylazetidin-3-one 6a (0.016 g,
0.039 mmol, 20%).
[3]
[4]
D. B. Huple, S. Ghorpade, R.-S. Liu, Adv. Synth. Catal. 2016, 358,
1348−1367.
a) A. Mukherjee, R. B. Dateer, R. Chaudhuri, S. Bhunia, S. N. Karad,
R.-S. Liu, J. Am. Chem. Soc. 2011, 133, 15372–15375; b) Y.-C. Hsu,
S.-A. Hsieh, P.-H. Li, R.-S. Liu, Chem. Commun. 2018, 54, 2114-2117.
a) R. L. Sahani, M. D. Patil, S. B. Wagh, R.-S. Liu, Angew. Chem., Int.
Ed. 2018, 57, 14878−14882; (b) H. Wei, M. Bao, K. Dong, L. Qiu, B.
Wu, W. Hu, X. Xu, Angew. Chem., Int. Ed. 2018, 57, 17200−17204.
R. L. Sahani, R.-S. Liu, ACS Catal. 2019, 9, 5890−5896.
5a. 1H NMR (600 MHz, CDCl3): δ 7.51 (d, J = 8.4 Hz, 2H), δ 7.48 (d, J =
8.4, 1H), δ 7.32 ~ 7.25 (m, 3H), δ 7.15 (d, J = 7.2 Hz, 2H), 7.11 (d, J =
8.4 Hz, 2H), δ 7.01 (t, J = 8.4 Hz, 1H), δ 6.94 (t, J = 8.4 Hz, 1H), δ 6.75
(d, J = 8.4 Hz, 1H), δ 6.67 (s, 1H), δ 6.19 (s,1H), δ 4.80 (d, J = 13.8 Hz,
2H), δ 2.30 (s, 3H); 13C NMR (150 MHz, CDCl3): δ 144.0, 137.2, 136.4,
134.4, 132.9, 131.2, 129.7, 129.4, 128.8, 127.3, 121.4, 120.9, 120.2,
109.9, 93.0, 75.3, 46.5, 21.4; FD+ calcd for C23H20N2O2S: 388.1245,
found: 388.1240.
[5]
[6]
[7]
a) B. Sabyasachi, J-C. Chang, R.-S Liu, Org Lett 2012,14, 5522-5525;
b) A. B. Cuenca, S. Montserrat, K. M. Hossain, G. Mancha, A. Lledos,
M.-S. Mercedes, G. Ujaque, G. Asensio, Org. Lett. 2009, 11, 4906-
4909; c) C.-W. Li, K. Pati, G. Y. Lin, S. M. A. Sohel, H. H. Hung, R.-S.
Liu, Angew. Chem. Int. Ed. 2010, 49, 9891-9894; d) Y. Wang, L. Ye, L.
Zhang, Chem. Commun. 2011, 47, 7815-7817.
6a. 1H NMR (600 MHz, CDCl3): δ 7.66 (d, J = 8.4 Hz, 2H), δ 7.35 ~ 7.30
(m, 6H), δ 7.28 ~ 7.26 (m,1H), δ 7.11 (t, J = 7.2 Hz, 2H), δ 6.69 (td, J =
7.2, 1.2 Hz, 1H), δ 6.59 (dd, J = 8.4, 1.2 Hz, 2H), δ 5.05 (d, J = 7.2 Hz,
1H), δ 4.99 (dd, J = 6.6, 3.6 Hz, 1H), δ 4.82 (t, J = 7.2 Hz, 1H), δ 4.4 (d, J
= 16.2 Hz, 1H) δ 4.28 (dd, J = 16.2 Hz, 4.2 Hz, 1H), δ 2.42 (s, 3H). 13C
NMR (150 MHz, CDCl3): 193.1, 145.0, 136.4, 129.2, 128.2, 127.7, 127.4,
127.2, 126.6, 117.5, 112.9, 86.1, 70.0, 56.9, 20.6. HRMS-ESI+ calcd for
C23H22N2O3S: 406.1346, found 406.1345.
[8]
[9]
For ligand effects in gold catalysis, see selected review: a) D. J. Gorin,
B. D. Sherry, F. D. Toste, Chem. Rev. 2008, 108, 3351-3378.
a) S. Kramer, F. Gagosz, In Gold Catalysis: An Homogeneous
Approach” F. D. Toste and V. Michellet Eds, chapter 1, pp 1-50,
Imperial College Press, 2014; b) P. Klahn, S. F. Kirsh, Chem..Cat.
Chem. 2011, 3, 649-652; c) M. R. Luzung, P. Mauleon, F. D. Toste, J.
Am. Chem. Soc. 2007, 129, 12402-12403; d) I. Alonso, B. Trillo, F.
López, S. Montserrat, G. Ujaque, L. Castedo, A. Lledós, J. L.
Mascareňas, J. Am. Chem. Soc. 2009, 131, 13020-13030; e) I. Alonso,
H. Faustino, F. Lopez, J. L. Mascareňas, Angew. Chem., Int. Ed. 2011,
50, 11496−11500. f) C.-D. Wang, Y.-F. Hsieh, R.-S. Liu, Adv. Synth.
Catal., 2014, 356, 144-152.
Acknowledgements
We thank the Ministry of Education (MOE 106N506CE1) and the
Ministry of Science and Technology (MOST 107-3017-F-007-
002), Taiwan, for financial support of this work.
[10] Crystallographic data of compounds 3l, 5f, 5l and 6a were deposited in
Cambridge Crystallographic Data Center: 3l (CCDC 2012689), 5f
(CCDC 2013824), 5l (CCDC 2023003), 6a (CCDC 2013420).
Keywords: Aminocyclizations • Azacyclic products • Carbene •
Propargyl alcohols • Propargyl amines
[11] The geometry optimizations and zero-point vibrational energy (ZPVE)
were carried out using the B3LYP-D3 functional with the LANL2DZ
basis set for Au and the 6-31G** basis set for the other atoms (denoted
as LACVP**). In order to obtain a more accurate electronic energy, we
performed single-point energy calculations based on the same
functional, but using a larger basis set, where Au was described with
LANL2TZ and the other atoms were described with the 6-
311++G**basis set. Solvation energies were calculated using the
CPCM implicit solvation model. The solvation calculations used the
B3LYP/LACVP** level of theory and the gas-phase optimized structures.
All calculations were performed using the Gaussian09 package.
[1]
Reviews for gold carbenes: a) A. S. K. Hashmi, Chem. Rev. 2007, 107,
3180−3211; b) L. Zhang, Acc. Chem. Res. 2014, 47, 877−888; c) H.-
S.Yeom, S. Shin, Acc. Chem. Res. 2014, 47, 966−977; d) Z. Zheng, Z.
Wang, Y. Wang, L. Zhang, Chem. Soc. Rev. 2016, 45, 4448−4458; e)Y.
Wang, M. E. Muratore, A. M. Echavarren, Chem. Eur. J. 2015, 21,
7332–7339; f) J. Xiao, X. Li, Angew. Chem. Int. Ed. 2011, 50, 7226–
7236; g) L. Ye, X-Q. Zhu, R. L. Sahani, Y. Xu, P-C. Qian, R.-S. Liu,
Chem. Rev. 2020, DOI: 10.1021/acs.chemrev.0c00348.
[2]
For the generation of α-oxo gold carbenes with N-O oxides; see
selected examples: a) L. Ye, L. Cui, G. Zhang, L. Zhang, J. Am. Chem.
Soc. 2010, 132, 3258−3259; b) L. Ye, W. He, L. Zhang, J. Am. Chem.
Soc.2010, 132, 8550−8551; (c) Y. Wang, Z. Zheng and L. Zhang, J. Am.
Chem. Soc., 2015, 137, 5316–5319; (d) G. Zhang, Y. Peng, L. Cui and
L. Zhang, Angew. Chem., Int. Ed., 2009, 48, 3112–3115; (e) Y. Wang,
K. Ji, S. Lan, L. Zhang, Angew. Chem. 2012, 124, 1951–1954; (f) B. Lu,
C. Li, L. Zhang, J. Am. Chem. Soc., 2010, 132, 14070–14072; (g) B. S.
Kale, R. S. Liu, Org. Lett. 2019, 21, 8434−8438; (h) A. P. Jadhav, S.
Bhunia, H.-Yi. Liao, R.-S. Liu, J. Am. Chem. Soc. 2011, 133, 1769–
1771; (i) C. Shu, L. Li, Y.-F. Yu, S. Jiang and L.-W. Ye, Chem.
Commun., 2014, 50, 2522–2525; (j) W. E. Brenzovich, Jr., D. Benitez,
[12] In Table 1, we isolated compound 4a in several gold catalysts.
Formation of 4a can be rationalized by an initial oxoarylation to form
species H’ that undergoes an intramolecular cyclization to yield product
4. This step is analogous to that for compound 5a. A further arylation of
compound 4 is expected to yield the observed product 4a.
6
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