Journal of the American Chemical Society
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reductive Cuꢀcatalyzed regiodivergent carboxylation of alꢀ
lenes using silylboranes as coupling partners.
Excellence Accreditation 2014ꢀ2018; SEVꢀ2013ꢀ0319) for
support. Johnson Matthey, Umicore and Nippon Chemical
Industrial are acknowledged for a gift of metal & ligand
sources. J.C thanks European Union (FP7ꢀPEOPLEꢀ2012ꢀ
IEFꢀ328381) for a fellowship. We thank Prof. V. Grushin,
Prof. D. Milstein & Prof. S. Ogoshi for useful discussions
and E. Escudero for XꢀRay crystallographic data. This paꢀ
per is dedicated to the memory of Prof. Greg L. Hillhouse.
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(12) For the carboxylation of allyl boronates, see: (a) Duong, H.
A.; Huleatt, P. B.; Tan, Q. –W.; Shuying, E. L. Org. Lett.
2013, 15, 4034. For the carboxylation of allyl stannanes: (b)
Hruszkewycz, D. P.; Wu, J.; Hazari, N.; Incarvito, C. D. J.
Am. Chem. Soc. 2011, 133, 3280. (c) Shi, M.; Nicholas, K.
M. J. Am. Chem. Soc. 1997, 119, 5057.
(13) For selected carboxylation of wellꢀdefined organometallics
derived from allyl halides: (a) Wu, J.; Green, J. C.; Hazari,
N.; Hruszkewycz, D. P. Incarvito, C. D.; Schmeier, T. J.
Organometallics 2010, 29, 6369. (b) Miao, B.; Ma, S.
Chem. Commun. 2014, 50, 3285. (c) Hung, T.; Jolly, P. W.;
Wilke, G. J. Organomet. Chem. 1980, 190, C5. (d) Courꢀ
tois, G.; Migniac, L. J. Organomet. Chem. 1974, 69, 1. (e)
Friederich, L. E.; Cormier, R. A. J. Org. Chem. 1971, 36,
3011.
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(3) For selected reviews on metalꢀcatalyzed allylic substitution:
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J. J. Org. Chem. 2012, 77, 9989. (c) Wang, S.; Qian, Q.;
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delec, J. –Y.; Perichon, J. J. Org. Chem. 1996, 61, 1748.
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(9) Maag, H. Prodrugs of Carboxylic Acids; Springer: New
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(10) For selected metalꢀcatalyzed regiodivergent reductive couꢀ
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(11) This work was presented at the 19th International Symposiꢀ
um on Homogeneous Catalysis, Ottawa (July 6ꢀ11, 2014).
At the conference, the Tsuji group described a non-
(14) See Supporting information for details.
(15) No products were detected under previously reported Niꢀ
catalyzed reductive carboxylation reactions (ref. 7b, 7c, 8c).
(16) For the beneficial role of MgCl2 in carboxylation reactions
or reductive events, see: (a) Wu, F.; Lu, W.; Qian, Q.; Ren,
Q.; Gong, H. Org. Lett. 2012, 14, 3044. (b) Metzger, A.;
Bernhardt, S.; Manolikakes, G.; Knochel, P. Angew. Chem.,
Int. Ed. 2010, 49, 4665. (c) Ref. 7c.
(17) Dimerization and reduction account for the mass balance.
The inclusion of H2O (10–100 mol%) shut down the reacꢀ
tivity.
(18) We found identical results when scaling up the reaction of
1a (1 mmol) under a L3 or L5 regime.
(19) Lower E/Z ratios were found for 2k-n, an observation that is
in line with the directing effect of tethered alkenes in Niꢀ
catalyzed coupling reactions. See for example: ref. 10d.
(20) For remarkable exceptions: (a) Luo, L.; Zhang, J. –J.; Ling,
W. –J.; Shao, Y. –L.; Wang, Y. –W.; Peng, Y. Synthesis
2014, 46, 1908. (b) Yang, D.; Belardi, J. K.; Micalizio, G.
C. Tetrahedron Lett. 2011, 52, 2144. (c) Refs. 7c and 8a
(21) No reaction took place when exposing 4,4ꢀdimethylpentꢀ1ꢀ
enꢀ3ꢀyl acetate possessing a quaternary carbon in αꢀposition
under the conditions based upon L5. Likewise, no reaction
was observed with cyclohexꢀ2ꢀenꢀ1ꢀyl acetate.
(22) At higher Ni/L3 loadings we observed 2j and 5ꢀexoꢀtrig
cyclization in a linear relationship, suggesting that a radicalꢀ
escapeꢀrebound mechanism could be operating. Indeed, the
reaction of 1j with Ni/L3 was inhibited by addition of radiꢀ
cal scavengers such as TEMPO or galvinoxyl. Intriguingly,
3j was the only observable product with Ni/L5, reinforcing
the notion that a different interplay operates for L5.
(23) In line with this notion, we found that racemic 3b was obꢀ
tained from (R)ꢀ1b (65% ee) under a Ni/L5 regime.
(24) Powers, D. C.; Anderson, B. L.; Nocera, D. G. J. Am. Chem.
Soc. 2013, 135, 18876.
(25) Taking into consideration the tetrahedral geometry for Ni(0)
complexes, the squareꢀplanar environment found for 5
might suggest that this complex would be best described as
a Ni(II) complex of a reduced quaterpyridine ligand dianion
or a Ni(I)ꢀL15 with an antiferromagnetic coupling. For an
excellent review dealing with redoxꢀactive ligands: Hu, X.
Chem. Sci. 2011, 2, 1867.
(26) The use of stoichiometric Ni(COD)2/L3 or Ni(COD)2/L5 in
provided otherwise identical reactivity to 4 and 5.
(27) Tridentate, pincerꢀtype ligands have shown to promote a
related αꢀbranched carboxylation of allenes. The mechaꢀ
nism is believed to proceed via the formation of a new CꢀC
bond between CO2 and the γꢀcarbon of an in situ generated
η1ꢀallyl metal complexes, see: (a) Suh, H.–W.; Guard, L.
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