ChemComm
Page 4 of 4
DOI: 10.1039/C6CC05713F
ARTICLE
Journal Name
afford distannylated species
protodestannylation.
H
, which leads to 45 upon opens perspectives for the smooth generation of vinylidene
carbenes16 from nitriles fitted with an alpha leaving group.
The formation of imino pyrrolidines 43 and 44 can be
explained by the release of tin amide in the reaction
L
Acknowledgements
medium, which acts as a nucleophile to the open starting
azetidine regioselectively at the quaternary center.15 This tin
The University of Versailles St-Quentin-en-Yvelines and the
CNRS are acknowledged for funding. PQ acknowledges l’École
polytechnique for a PhD grant.
amide would be produced from
through a vinylogous elimination step (
amino nitrile then leads to through intramolecular
J
, the tautomeric form of
I,
J
ꢀK). Thus produced
M
N
nucleophilic addition, and next to (Z)-43 or 44 upon N-
acylation with Boc2O.
Notes and references
1
(a) F. Alonso, I. P. Beletskai, M. Yus, Chem. Rev. 2004, 104,
Scheme 8: Possible mechanisms for the formation of 43-45
3079. (b) B. E. Maryanoff, H. C. Zhang, J. H. Cohen, I. J.
Turchi, C. A. Maryanoff, Chem. Rev. 2004, 104, 1431. (c) F.
Ferreira, C. Botuha, F. Chemla, A. Perez-Luna, J. Org. Chem.
2009, 74, 2238. (d) Y. Song, S. Okamoto, F. Sato,
Tetrahedron Lett. 2002, 43, 8635. (e) R. Kumareswaran, J.
Galluci, T. V. RajanBabu, J. Org. Chem. 2004, 69, 9151. (f) D.
R. Fandrick, C. S. Johson, K. R. Fandrick, J. T. Reeves, Z. Tan,
H. Lee, J. J. Song, N. K. Yee, C. H. Senanayake, Org. Lett.
2010, 12, 748. (g) H. Kim, Y. H. Rhee, J. Am. Chem. Soc.
2012, 134, 4011. (h) A. Varela-Fernandez, J. A. Varela, C.
Saa, Synthesis, 2012, 44, 3285. (i) J. H. Lee, C. Kim, Y. H.
Rhee, Bull. Korean Chem. Soc. 2011, 32, 2867.
2
(a) A. Z. Gonzales, J. A. Soderquist, Org. Lett. 2007,
(b) S. Kobayashi, T. Kitanosono, M. Ueno, Synlett 2010,
2033. (c) H. M. Wisniewska, E. R. Jarvo, Chem. Sci. 2011,
9, 1081.
2,
807. (d) R. A. Brawn, J. S. Paneck, Org. Lett. 2009, 11, 4362.
(e) A. Yanagisawa, T. Suzuki, T. Koide, S. Okitsu, T. Arai,
Chem. Asian J. 2008, 3, 1793. (f) T. Thaima, S. G. Pyne, Org.
Lett. 2015, 17, 778. (g) T. Guo, R. Song, B-H. Yuan, X-Y. Chen,
X-W. Sun, G-Q. Lin, Chem. Commun. 2013, 49, 5402.
E. M. Vieira, F. Haeffner, M. L. Snapper, A. H. Hoveyda,
Angew. Chem. Int. Ed. 2012, 51, 6618.
(a) C. Agami, F. Couty, G. Evano, Tetrahedron: Asymmetry,
2002, 13, 297. (b) P. Quinodoz, B. Drouillat, K. Wright, J.
Marrot, F. Couty J. Org. Chem. 2016, 81, 2899.
3
4
5
For a review on this topic, see: F. Couty, B. Drouillat, G.
Evano, O. David, Eur. J. Org. Chem. 2013, 11, 2045. A.
Hartikka, P. I. Arvidsson, Eur. J. Org. Chem. 2005, 4287.
A. Hartikka, P. I. Arvidsson, Eur. J. Org. Chem. 2005, 4287.
(a) Kyowa Hakko Kogyo Co., Ltd Patent EP 1988091 A1,
2008. (b) Van Nhien A. N.; Postel, L. R. ; Carmo Carreiras,
M. ; García, A. G. ; Marco-Contelles, J. J. Carbohydr. Chem.
2005, 24, 369-377.
6
7
This compounds then slowly isomerizes to the (E)-isomer,
stabilized by an intramolecular H-bond between the
secondary amine and the oxygen atom of the C=O moiety of
the Boc group (see X-ray data in supplementary material).
Thus, the different outcome in this reaction involving
quaternary azetidines seems to be correlated with the
8
9
Structure 43 was deposited at the Cambridge database and
was allocated number CCDC 1452925
D. Cantillo, B. Gutmann, C. O. Kappe, J. Am. Chem. Soc.
2011, 133, 4465.
.
increased lifetime of the intermediate tetrazafulvene
I (R =
10 Concerted or stepwise mechanism for this decomposition is
not documented in literature.
11 R. Knorr, Chem. Rev. 2004, 104, 3795.
Me, Ph, Scheme 8) compared to B (Scheme 7) which leads
more rapidly to the vinylidene carbene.
12 (a) D. J. Wardrop, J. P. Komenda, Org. Lett. 2012, 14, 1548.
(b) P. Quinodoz, C. Lo, M. Kletskii, O. Burov, J. Marrot, F.
Couty, Org. Chem. Front. 2015, 2, 492.
Conclusions
13 Temperatures above 100°C are usually required to conduct
such cycloadditions, see for example: M. J. Schulz, S J..
Coats, D. J. Hlasta, Org. Lett. 2004, 6, 3265.
14 Tetrazoles are probably formed in all cases, but they were
isolated only in the cases of 33-35, due to precipitation and
easy isolation.
15 Azetidinium ions are opened regioselectively at the
quaternary position, see: B. Drouillat, K. Wright, O. David, F.
Couty, Eur. J. Org. Chem. 2012, 30, 6005.
In conclusion, we have reported a new procedure to prepare
homopropargyl amines which complements the existing ones.
A close examination of the scope of this reaction gave
interesting insights into the mechanism of decomposition of
tetrazafulvenes into vinylidene carbenes. This less studied
aspect of the chemistry of functionalized tetrazoles is
presently under active investigation in our group since it
16 Grainger, R. S.; Munro, K. R. Tetrahedron, 2015, 71, 7795.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx