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favourable for a sterically hindered alkenyl end (R = R’ = Me).
Tang, Org. Biomol. Chem., 2009, 7,DO3I3: 1301.1-303393/7C;6CeC)04V3.08NA.
Lindsay, D. Fiset, P. J. Gritsch, S. Azzi, A. B. Charette, J. Am.
Gold-catalyzed 8a
process, based on their reaction durations (18 h versus 12 h,
eq 5). Accordingly, alkylidenecyclopropane species 8a (or ) is
unlikely to be a primary precursor to generate the key
→7a conversion is slower than the 5a→7a
Chem. Soc., 2013, 135, 1463-1470
.
A
7
(a) L. Zhang, Acc. Chem. Res., 2014, 47, 877-888; (b) A. S. K.
Hashmi, Angew. Chem. Int. Ed., 2008, 47, 6754-6756; (c) S.
Bhunia, R.-S. Liu, J. Am. Chem. Soc., 2008, 130, 16488-16489;
(d) D. Benitez, N. D. Shapiro, E. Tkatchouk, Y. Wang, W. A.
aminoallylic cation
excluded.
E although its participation cannot be
Goddard III, F. D. Toste, Nature Chemistry, 2009, 1, 482-486;
Before this work, metal-catalyzed reactions of α-aryl
(e) G. Seidel, R. Mynott, A. Fürstner, Angew. Chem. Int. Ed.,
2009, 48, 2510-2513; (f) E. Jiménez-Núñez, C. K. Clavarie, C.
Bour, C. D. J. Cardenas, A. M. Echavarren, Angew. Chem. Int.
Ed., 2008, 47, 7892-7895.
diazoesters[12] with internal alkynes and allenes proceed
exclusively via
a cyclopropenation or cyclopropanation
mode.[1-3] In this work, we report the realization of [3+2]-
annulations of ynamides and allenamides[13] with
diazocyanides using suitable gold catalysts. An effective scope
of α-aryl diazocyanides, internal ynamides and allenamides is
compatible with such [3+2]-annulations. Our experimental
data exclude the intermediacy of cyclopropenes for the
8
9
(a) S. Chuprakov, V. Gevorgyan, Org. Lett., 2007, 9, 4463-
4466; b) J. T. Bauer, M. S. Hadfield, A.-L. Lee, Chem.
Commun., 2008, 6405-6407; c) M. S. Hadfield, L. Jonas, L.
Haller, A.-L. Lee, S. A. Maegregor, J. A. T. O’neill, A. M.
Watson, Org. Biomol. Chem., 2012, 10, 4433-4440.
x-ray crystallographic data of compounds 3a’, 4a, 7a and 6d
were deposited in Cambridge Crystallographic Data Center:
3a’, CCDC 1469310; 4a CCDC 1469309; 7a 1469306 and 6d
1469307.
reactions
of
internal
ynamides
whereas
alkylidenecyclopropanes are likely involved in the allenamide
reactions. Further utility of these resulting 1-amino-1H-
Indenes for synthesis of bioactive molecules is under future
investigation.[14]
10 For gold-catalyzed [3+2]-carbocycloadditions of allenylamides
with other carbon electrophiles, see: a) Y. Wang, P. Zhang, D.
Qian, J. Zhang, Angew. Chem. Int. Ed., 2015, 54, 14849-
14852; b) E. López, J. Gonzalez, L. A. López, Adv. Synth.
Catal., 2016, 358, 1428-1432.
11 See selected examples: a) B. Liu, Y. Fan, Y. Gao, C. Sun, C. Yu,
J. Zhu, J. Am. Chem. Soc., 2013, 135, 468-473; b) E. Clot, M.
Besora, F. Baseras, C. Megret, O. Einstein, B. Oelckers, R. N.
Perutz, Chem. Commun., 2003, 490-491; c) M. E. Evans, C. L.
Burke, S. Yaihuathes, E. Clot, O. Eisenstein, W. D. Jones, J.
Am. Chem. Soc., 2009, 131, 13464-13473.
Notes and references
1
a) M. P. Doyle, In Comprehensive Organometallic Chemistry
II, E. W. Abel, F. G. A. Stone, Ed.; Pergamon: Oxford UK, vol
12, 387-469; b) M. P. Doyle, M. A. McKervy, T. Ye, Modern
Catalytic Method for Organic Synthesis with Diazo
Compounds: From Cyclopropanes to Ylides; Wiley; New York,
1998; c) H. M. L. Davies; R. E. J. Beckwith, Chem. Rev., 2003,
12 For gold-carbenes generated from the decomposition of α-
diazo esters, see selected examples: a) M. R. Fructos, T. R.
Belderrain, P. de Fremont, N. M. Scott, S. P. Nolan, M. M.
103, 2861-2903; d) Z. Zhang, J. Wang, Tetrahedron, 2008, 64
,
6577-6605; e) L. Liu, J. Zhang, Chem. Soc. Rev., 2016, 45, 506-
516; f) S. P. Nolan, Acc. Chem. Res., 2011, 44, 91-100.
Diaz-Requejo, P. J. Perez, J. Am. Chem. Soc., 2004, 126
,
2
For chemistry of cyclopropene compounds, see selected
reviews: a) A. Padwa, Acc. Chem. Res., 1979, 12, 310-312; b)
10846-10847. b) M. R. Fructos, T. R. Belderrain, M. C.
Nicasio, S. P. Nolan, H. Kaur, M. M. Dıaz-Requejo, P. J. Perez,
Angew. Chem. Int. Ed., 2005, 44, 5284-5288; c) Z. Yu, B. Ma,
M. Chen, H.-H. Wu, L. Liu, J. Zhang, J. Am. Chem. Soc., 2014,
136, 6904-6907; d) J. Barluenga, G. Lonzi, M. Tomas, L. A.
Lopez, Chem. Eur. J., 2013, 19, 1573-1576; e) D. Zhang, G. Xu,
M. Rubin, M. Rubina, V. Gevorgyan, Chem. Rev., 2007, 107
,
3117-3179; c) R. Walsh, Chem. Soc. Rev., 2005, 34, 714-732;
d) M. S. Baird, Chem. Rev., 2003, 103, 1271-1294.
For the utility of alkylidenecyclopropane derivatives, see
recent reviews: a) A. Brandi, S. Cicchi, F. M. Cordero, A. Goti,
Chem. Rev., 2014, 114, 7317-7420; b) D.-H. Zhang, X.-Y. Tang,
M. Shi, Acc. Chem. Res., 2014, 47, 913-924.
3
4
D. Ding, C. Zhu, J. Li, J. Sun, Angew. Chem. Int. Ed., 2014, 53
,
11070-11074; f) G. Lonzi, L. A. Lopez, Adv. Synth. Catal.,
2013, 355, 1948-1954; g) V. V. Pagar, A. M. Jadhav, R.-S. Liu,
J. Am. Chem. Soc., 2011, 133, 20728-20731; h) A. M. Jadhav,
V. V. Pagar, R.-S. Liu, Angew. Chem. Int. Ed., 2012, 51, 11809-
11813; i) V. V. Pagar, R.-S. Liu, Angew. Chem. Int. Ed., 2015,
54, 4923-4926.
Rh: a) V. N. G. Lindsay, D. Fiset, P. J. Gritsch, S. Azzi, A. B.
Charette, J. Am. Chem. Soc., 2013, 135, 1463-1470; b) H. M. L.
Davis, G. H. Lee, Org. Lett., 2004, 13, 2117-2120; c) A.
Edwards, M. Rubin, Tetrahedron, 2015, 71, 3237-3246; d) J. R.
Denton, K. Cheng, H. M. L. Davies, Chem. Commun., 2008,
1238-1240; e) F. G. Adly, M. G. Gardniner, A. Ghanem, Chem.
Eur. J., 2016, 22, 3447-3461; Cu: f) A. K. Swenson, K. E.
Higgins, M. G. Brewer, W. W. Brennessel, M. G. Coleman,
Org. Biomol. Chem., 2012, 10, 7483-7486; g) T. J. Thomas, B.
A. Merritt, B. E. Lemma, A. M. Mckoy, T. N. Nguyen, A. K.
Swenson, J. L. Mills, M. G. Coleman, Org. Biomol. Chem.,
2016, 14, 1742-1747; Ag: h) J. F. Briones, H. M. L. Davis, Org.
Lett., 2011, 13, 3984-3987; Co: i) X. Cui, X. Xu, H. Lu, S. Zhu, L.
Wojtas, X. P. Zhang, J. Am. Chem. Soc., 2011, 133, 3304-3307;
Ir: j) M. Uehara, H. Suematsu, Y. Yasutomi, T. Katsuki, J. Am.
Chem. Soc., 2011, 133, 170-171; Au: k) J. F. Briones, H. M. L.
Davis, J. Am. Chem. Soc., 2012, 134, 11916-11919.
13 Reviews for ynamides and allenynamides, see: (a) X.-N.
Wang, H.-S. Yeom, L.-C. Fang, S. He, Z.-X. Ma, B. L. Kedrowski,
R. P. Hsung, Acc. Chem. Res., 2014, 47, 560-578; (b) K. A.
DeKorver, H. Li, A. G. Lohse, R. Hayashi, Z. Lu, Y. Zhang, R. P.
Hsung, Chem. Rev., 2010, 110, 5064-5106; (c) G. Evano, A.
Coste, K. Jouvin, Angew. Chem. Int. Ed., 2010, 49, 2840-2859;
(d) G. Evano, C. Theunissen, M. Lecomte, Aldrichimica Acta,
2015, 48, 59; e) T. Lu, Z. Lu, Z.-X. Ma, Y. Zhang, R. P. Hsung,
Chem. Rev., 2013, 113, 4862-4904.
14 For natural products containing 1-aminoindane cores, see a)
C. Binda, F. Hubalek, M. Li, J. Sterling, D. E. Edmondson, A.
Mattevi, J. Med. Chem., 2005, 48, 8148-8154; b) O. Rascol, J.
D. Brooks, E. Melamed, F. Stocchi, E. Tolosa Lancet, 2005,
365, 947-954; c) C. Binda, F. Hubalek, M. Li, J. Sterling, D. E.
Edmondson, A. Mattevi; J. Med. Chem., 2005, 48, 8148-8154;
5
6
E. J. Park, S. H. Kim, S. Chang, J. Am. Chem. Soc., 2008, 130,
17268-17269.
See selected examples: a) T. M. Gregg, M. K. Farrugia, J. R.
Frost, Org. Lett., 2009, 11, 4434-4436; b) C. C. Huval, D. A.
Singleton, J. Org. Chem., 1994, 59, 2020-2024; c) S. Ma, J.
Zhang. Angew. Chem. Int. Ed., 2003, 42, 183-187; d) T. Lu, R.
d) S. Tian, W. Zi, D. Ma; Angew. Chem. Int. Ed., 2012, 51
10141-10144.
,
4 | J. Name., 2012, 00, 1-3
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