Journal of the American Chemical Society
Page 8 of 10
Eur. J. Org. Chem. 2014, 4925ꢀ4948. (c) Trost, B. M.; Zhang, T.;
Importantly, DFT calculations have revealed the rationale of
the excellent stereocontrol in these transformations and the
transition state t(4-5)‡, with a lower barrier, leading to a (Z)ꢀ
configured sixꢀmembered palladacycle t5 was computed as a
crucial intermediate towards a kinetic differentiation between
the pathways leading to either the (E) or (Z) product, with
Pd−O chelation as a stabilizing structural feature. This latter
feature guides the process towards the formation of a (Z)ꢀ
configured allylic amine. The DFT studies reported here add
crucial information with respect to the mechanistic underꢀ
standing in decarboxylative functionalization of vinyl carꢀ
bonates, and differentiates from a previously postulated zwitꢀ
terionic species.9 This new mode of stereocontrol provides
further synthetic potential for the functionalization of allylic
surrogates, giving prospectively access to various types of
stereopure and functionalized olefin building blocks being of
general synthetic interest.
Sieber, J. D. Chem. Sci. 2010, 1, 427ꢀ440. See for representative
contributions using allylic linear carbonates: (d) Leitner, A.; Shu, C.;
Hartwig, J. F. Org. Lett. 2005, 7, 1093ꢀ1096. (e) MorenoꢀMañas, M.;
Morral, L.; Pleixats, R. J. Org. Chem. 1998, 63, 6160ꢀ6166. (f)
Leitner, A.; Shekhar, S.; Pouy, M. J.; Hartwig, J. F. J. Am. Chem. Soc.
2005, 127, 15506ꢀ15514. (g) Shekhar, S.; Trantow, B.; Leitner, A.;
Hartwig, J. F. J. Am. Chem. Soc. 2006, 128, 11770ꢀ11771. (h)
Plietker, B. Angew. Chem. Int. Ed. 2006, 45, 6053ꢀ6056; For direct
use of allylic alcohols: (i) Das, K.; Shibuya, R.; Nakahara, Y.; Gerꢀ
main, N.; Ohshima, T.; Mashima, K. Angew. Chem. Int. Ed. 2012, 51,
150ꢀ154. (j) Gumrukcu, Y.; de Bruin, B.; Reek, J. N. H.
ChemSusChem 2014, 7, 890ꢀ896. (k) Yang, S.ꢀC.; Tsai, Y.ꢀC.
Organometallics 2001, 20, 763ꢀ770. (l) Kinoshita, H.; Shinokubo, H.;
Oshima, K. Org. Lett. 2004, 6, 4085ꢀ4088. (m) Ghosh, R.; Sarkar, A.
J. Org. Chem. 2011, 76, 8508ꢀ8512. (n) Ohshima, T.; Miyamoto, Y.;
Ipposhi, J.; Nakahara, Y.; Utsunomiya, M.; Mashima, K. J. Am.
Chem. Soc. 2009, 131, 14317ꢀ14328. Miscellaneous examples: (o)
Pace, V.; Martínez, F.; Fernádez, M.; Sinisterra, J. V.; Alcántara, A.
R. Org. Lett. 2007, 9, 2661ꢀ2664. (p) Dubovyk, I.; Watson, I. D. G.;
Yudin, A. K. J. Org. Chem. 2013, 78, 1559ꢀ1575. (q) Adak, L.; Chatꢀ
topadhyay, K.; Ranu, B. C. J. Org. Chem. 2009, 74, 3982ꢀ3985.
(4) See for representative examples: (a) Banerjee, D.; Junge, K.;
Beller, M. Angew. Chem. Int. Ed. 2014, 53, 1630ꢀ1635. (b) Banerjee,
D.; Junge, K.; Beller, M. Org. Chem. Front. 2014, 1, 368ꢀ372. (c) Yi,
C. S.; Yun, S. Y. Org. Lett. 2005, 7, 2181ꢀ2183. (d) Minami, T.;
Okamoto, H.; Ikeda, S.; Tanaka, R.; Ozawa, F.; Yoshifuji, M. Angew.
Chem. Int. Ed. 2001, 40, 4501ꢀ4503. (e) Qin, H.; Yamagiwa, N.;
Matsunaga, S.; Shibasaki, M. J. Am. Chem. Soc. 2006, 128, 1611ꢀ
1614.
(5) This methodology generally requires stoichiometric amounts of
external oxidant: (a) Reed, S. A.; White, M. C. J. Am. Chem. Soc.
2008, 130, 3316ꢀ3318. (b) Yin, G.; Wu, Y.; Liu, G. J. Am. Chem. Soc.
2010, 132, 11978ꢀ11987. (c) Sharma, A.; Hartwig, J. F. J. Am. Chem.
Soc. 2013, 135, 17983ꢀ17989. (d) Paradine, S. M.; Griffin, J. R.;
Zhao, J.; Petronico, A. L.; Miller, S. M.; White, M. C. Nat. Chem.
2015, 7, 987ꢀ994. (e) C. C. Pattillo, I. I. Strambeanu, P. Calleja, N. A.
Vermeulen, T. Mizuno, M. C. White, J. Am. Chem. Soc. 2016, 138,
1265–1272.
(6) Formation of γꢀdisubstituted allylic amines with two different
substituents has been seldom achieved and only with poor stereoꢀ
selectivities and quite limited scope. Examples through diamination of
dienes: (a) Martínez, C.; Martínez, L.; Kirsch, J.; EscuderoꢀAdán, E.
C.; Martin, E.; Muñiz, K. Eur. J. Org. Chem. 2014, 2017ꢀ2021. (b)
Lishchynskyi, A.; Muñiz, K. Chem. Eur. J. 2012, 18, 2212ꢀ2216.
Also see ref. 4a and 4b. Through allylic substitution reactions, see
reference 3m.
(7) (a) Hikawa, H.; Yokoyama, Y. Org. Biomol. Chem. 2011, 9,
4044ꢀ4050. (b) Yokoyama, Y.; Takagi, N.; Hikawa, H.; Kaneko, S.;
Tsubaki, N.; Okuno, H. Adv. Synth. Catal. 2007, 349, 662ꢀ668. (c)
Ramanathan, B.; Odom, A. L. J. Am. Chem. Soc. 2006, 128, 9344ꢀ
9345. (d) Zeng, X.; Soleilhavoup, M.; Bertrand, G. Org. Lett. 2009,
11, 3166ꢀ3169. Similar approaches have also been used in the syntheꢀ
sis of other alkene scaffolds, see for example: (e) Trost, B. M.; Malꢀ
hotra, S.; Chan, W. H. J. Am. Chem. Soc. 2011, 133, 7328ꢀ7331. (f)
Fang, X.; Li, H.; Jackstell, R.; Beller, M. J. Am. Chem. Soc. 2014,
136, 16039ꢀ16043.
(8) (a) Hussain, N.; Hussain, M. M.; Ziauddin, M.; Triyawatanyu,
P.; Walsh, P. J. Org. Lett. 2011, 13, 6464ꢀ6467. (b) Tonogaki, K.;
Itami, K.; Yoshida, J. J. Am. Chem. Soc. 2006, 128, 1464ꢀ1465. (c)
Xie, M.; Sun, Y.; Zhang, W.; Gu, X.; Zhao, X.; Xie, F.; Wang, S.
Synth. Commun. 2008, 38, 3785ꢀ3796. (d) Patel, S. J.; Jamison, T. F.
Angew. Chem. Int. Ed. 2004, 43, 3941ꢀ3944. (e) By nonꢀcatalytic
allylic substitutions: Sen, S. E.; Roach, S. L. Synthesis, 1995, 7, 756ꢀ
758. (f) Anumandla, D.; Littlefield, R.; Jeffrey, C. S. Org. Lett. 2014,
16, 5112ꢀ5115.
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ꢀ ASSOCIATED CONTENT
Supporting Information. Experimental details for the carbonate
substrate synthesis, copies of relevant NMR and IR spectra of all
allylic amine products, Xꢀray data in cif format, computational
details, summary of alternative computed mechanisms and Carteꢀ
sian coordinates of all optimized structures. This material is availꢀ
collection of computational results is available in the iochemꢀdb
database.32
ꢀ AUTHOR INFORMATION
Corresponding Author
* akleij@iciq.es; fmaseras@iciq.es
Notes
The authors declare no competing financial interest.
ꢀ ACKNOWLEDGEMENTS
We thank ICIQ, ICREA, and the Spanish Ministerio de Economía
y Competitividad (MINECO) through projects CTQꢀ2014–57661ꢀ
R and CTQꢀ2014–60419ꢀR, and the Severo Ochoa Excellence
Accreditation 2014–2018 through project SEVꢀ2013–0319. FM
and AWK also acknowledge support from RedINTECAT
(CTQ2014ꢀ52974ꢀREDC). Dr. Noemí Cabello, Sofía Arnal, and
Vanessa Martínez are acknowledged for the mass analyses. WG
thanks the Cellex foundation for funding of a postdoctoral fellowꢀ
ship. We sincerely thank Dr. Alexandr Shafir for useful discusꢀ
sions.
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