Organic & Biomolecular Chemistry
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ARTICLE
DOI: 10.1039/C4OB01627K
Hossaini, F. Amiri and E. Assadpour, Eur. J. Med. Chem., 2009, 44
,
12 The reported selectivity4h was also reproduced under the same
reaction conditions using CsF in MeCN at rt (see the Supplementary
Information).
3064−3067; (d) D. Patel, M. Jain, S. R. Shah, R. Bahekar, P. Jadav,
B. Darji, Y. Siriki, D. Bandyopadhyay, A. Joharapurkar, S.
Kshirsagar, H. Patel, M. Shaikh, K. V. V. M. Sairam and P. Patel, 13 For selected examples of 4ꢀsubstitutedꢀgroupꢀdirected benzyne
ChemMedChem, 2011,
6
, 1011−1016; (e) A. Dubey, S. K. Srivastava
reaction, see: (a) H. Yoshida, Y. Honda, E. Shirakawa and T.
and S. D. Srivastava, Bioorg. Med. Chem. Lett., 2011, 21, 569−573.
(a) T. Matsumoto, T. Sohma, S. Hatazaki and K. Suzuki, Synlett
1993, 843−846; (b) T. Jin and Y. Yamamoto, Angew. Chem. Int. Ed.
Hiyama, Chem. Commun., 2001, 1880–1881; (b) H. Yoshida, H.
4
,
,
Fukushima, J. Ohshita and A. Kunai, J. Am. Chem. Soc., 2006, 128
11040–11041; (c) Z. Liu and R. C. Larock, J. Org. Chem., 2006, 71
,
,
2007, 46, 3323−3325; (c) F. Shi, J. P. Waldo, Y. Chen and R. C.
Larock, Org. Lett., 2008, 10, 2409−2412; (d) Z. Liu, F. Shi, P. D. G.
3198–3209; (d) C. Raminelli, Z. Liu and R. C. Larock, J. Org. Chem.
,
2006, 71, 4689–4691; (e) H. Yoshida, T. Morishita, H. Fukushima, J.
Martinez, C. Raminelli and R. C. Larock, J. Org. Chem., 2008, 73
,
Ohshita and A. Kunai, Org. Lett., 2007, 9, 3367–3370; (f) J. D.
219−226; (e) M. Dai, Z. Wang and S. J. Danishefsky, Tetrahedron
Lett., 2008, 49, 6613−6616; (f) L. CampbellꢀVerduyn, P. H. Elsinga,
Kirkham, P. M. Delaney, G. J. Ellames, E. C. Row and J. P. A.
Harrity, Chem. Commun., 2010, 46, 5154–5156; (g) E. Yoshioka and
H. Miyabe, Tetrahedron, 2012, 68, 179–189; (h) H. Yoshida, R.
Yoshida and K. Takaki, Angew. Chem. Int. Ed., 2013, 52, 8629–
8632.
L. Mirfeizi, R. A. Dierckx and B. L. Feringa, Org. Biomol. Chem.
2008, , 3461−3463; (g) F. Zhang and J. E. Moses, Org. Lett., 2009,
11, 1587−1590; (h) J. A. Crossley and D. L. Browne, Tetrahedron
,
6
Lett., 2010, 51, 2271–2273; (i) C. Spiteri, C. Mason, F. Zhang, D. J. 14 All calculations were performed using the Gaussian 09 program
Ritson, P. Sharma, S. Keeling and J. E. Moses, Org. Biomol. Chem.
2010, , 2537–2542; (j) C. Spiteri, S. Keeling and J. E. Moses, Org.
Lett., 2010, 12, 3368−3371; (k) A. V. Dubrovskiy and R. C. Larock,
,
package (revision D.01): M. J. Frisch et al. Gaussian, Inc.:
Wallingford CT, 2009. For details, see the Supplementary
Information.
8
Org. Lett., 2010, 12, 1180−1183; (l) P. Li, J. Zhao, C. Wu, R. C. 15 For a natural bond orbital (NBO) method, see: (a) K. B. Wiberg,
Larock and F. Shi, Org. Lett., 2011, 13, 3340−3343; (m) Y. Fang, C.
Wu, R. C. Larock and F. Shi, J. Org. Chem., 2011, 76, 8840−8851;
(n) C. Lu, A. V. Dubrovskiy and R. C. Larock, J. Org. Chem., 2012,
Tetrahedron, 1968, 24, 1083–1096; (b) J. P. Foster and F. Weinhold,
J. Am. Chem. Soc., 1980, 102, 7211–7218; (c) A. E. Reed, R. B.
Weinstock and F. Weinhold, J. Chem. Phys., 1985, 83, 735–746.
77, 2279−2284; (o) A. V. Dubrovskiy, P. Jain, F. Shi, G. H. 16 For NBO6, see: E. D. Glendening, J. K. Badenhoop, A. E. Reed, J. E.
Lushington, C. Santini, P. Porubsky and R. C. Larock, ACS Comb.
Sci., 2013, 15, 193−201.
Carpenter, J. A. Bohmann, C. M. Morales and F. Weinhold,
Theoretical Chemistry Institute, University of Wisconsin, Madison,
2013.
5
For selected reviews on specific benzyne reactions, see: (a)
Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. 17 The natural “localized” molecular orbital (NLMO) based on the
Fleming and M. F. Semmelhack), Pergamon, Oxford, 1992, pp. 483–
515; (b) A. V. Dubrovskiy, N. A. Markina and R. C. Larock, Org.
Biomol. Chem., 2013, 11, 191–218; (c) S. A. Worlikar and R. C.
Larock, Curr. Org. Chem., 2011, 15, 3214–3232.
natural bond orbital (NBO) interpretations could give chemists actual
chemical and even quantitative insights without methodology/basis
setꢀdependency. For a review on NBO analysis, see: A. E. Reed, L.
A. Curtiss, and F. Weinhold, Chem. Rev., 1988, 88, 899–926.
6
7
(a) A. E. Goetz and N. K. Garg, Nature Chem., 2013, 5, 54–60; (b) A. 18 For recent reports on the NBO analysis of benzynes, see: (a) A.
E. Goetz and N. K. Garg, J. Org. Chem., 2014, 79, 846–851.
Takagi, T. Ikawa, Y. Kurita, K. Saito, K. Azechi, M. Egi, Y. Itoh, H.
Tokiwa, Y. Kita and S. Akai, Tetrahedron, 2013, 69, 4338–4352; (b)
A. Takagi, T. Ikawa, K. Saito, S. Masuda, T. Ito and S. Akai, Org.
Biomol. Chem., 2013, 11, 8145–8150.
(a) S. D. Ramgren, A. L. Silberstein, Y. Yang and N. K. Garg,
Angew. Chem. Int. Ed., 2011, 50, 2171–2173; (b) T. K. Macklin and
V. Snieckus, Org. Lett., 2005, 7, 2519–2522; (c) A. G. Sergeev and J.
F. Hartwig, Science, 2011, 332, 439–443; (d) T. Mesganaw, N. F. 19 Electron density ρ i of the
ith (reacting π) NBO of carbon atom CA
A
C
Fine Nathel and N. K. Garg, Org. Lett., 2012, 14, 2918–2921.
(A = 1 or 2) was evaluated as follows,
8
9
(a) T. Ikawa, H. Tokiwa and S. Akai, J. Synth. Org. Chem. Jpn.,
ρ i
=
ni
×
dC
(1)
A
A
C
2012, 70, 1123−1133; (b) T. Ikawa, A. Takagi, M. Goto, Y. Aoyama,
Y. Ishikawa, Y. Itoh, S. Fujii, H. Tokiwa and S. Akai, J. Org. Chem.
2013, 78, 2965–2983.
,
where ni is occupancy of the
ith NBO and dC is percentage
A
contribution from each carbon atom CA for the
ith NBO (Fig. 1).
For selected reviews on crossꢀcoupling of aryl triflates, see: (a) K. 20 Distortion analysis21 could also rationalize the regioselectivities of
Ritter, Synthesis, 1993, 735–762; (b) I. Baraznenok, V. Nenajdenko
and E. Balenkova, Tetrahedron, 2000, 56, 3077–3119; (c) Z. Gilson
and R. C. Larock, Chem. Rev., 2006, 106, 4644–4680.
(3+2) cycloaddition of 3ꢀsubstituted benzynes 3c and 3d; however,
this method could not be applied to the reactions of 4ꢀsubstituted
benzynes 3e and 3f (see the Supplementary Information).
10 For a related benzyne precursor, see: Y. Himeshima, T. Sonoda and 21 Recently, Houk and Garg et al. have proposed that distortions of
H. Kobayashi, Chem. Lett., 1983,
8
, 1211–1212.
arynes are useful to predict and understand the regioselectivities of
aryne reactions, see: (a) P. H.ꢀY. Cheong, R. S. Paton, S. M. Bronner,
GꢀY. J. Im, N. K. Garg and K. N. Houk, J. Am. Chem. Soc., 2010,
132, 1267–1269; (b) GꢀY. Im, S. M. J. Bronner, A. E. Goetz, R. S.
Paton, P. H.ꢀY. Cheong, K. N. Houk and N. K. Garg, J. Am. Chem.
Soc., 2010, 132, 17933–17944; (c) S. M. Bronner, J. L. Mackey, K.
11 (a) J. W. Bode, Y. Hachisu, T. Matsuura and K. Suzuki, Tetrahedron
Lett., 2003, 44, 3555–3558; (b) J. W. Bode, Y. Hachisu, T. Matsuura
and K. Suzuki, Org. Lett., 2003,
5, 391–394; (c) T. Matsuura, J. W.
Bode, Y. Hachisu and K. Suzuki, Synlett, 2003, 1746–1748.
6 | J. Name., 2012, 00, 1-3
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