Organometallics
Article
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(d) Gai, Y.; Julia, M.; Verpeaux, J.-N. Nickel-Catalyzed Cyclo-
propanation of Alkenes via Methylene Transfer from Lithiated tert-
Butyl Methyl Sulfone. Synlett 1991, 1991, 56−57.
ylide carbon is sp3-hybridized: Heydenreich, F.; Mollbach, A.; Wilke,
G.; Dreeskamp, H.; Hoffmann, E. G.; Schroth, G.; Seevogel, K.;
Stempfle, W. Stevensanaloge, Durch Nickelkomplexe Katalysierte
Umlagerung Von Triarylphosphoryliden Und Darstellung Sowie
Strukturbestimmung Von Phosphorylid-Nickeltricarbonylkomplexen.
Isr. J. Chem. 1972, 10, 293−319. (b) Additionally, computational
studies by our group have shown that the anionic carbon of the N-
ylide is tetrahedral with or without coordination to Li: den Hartog, T.;
Sarria Toro, J. M.; Couzijn, E. P. A.; Chen, P. A lithiomethyl
trimethylammonium reagent as a methylene donor. Chem. Commun.
2014, 50, 10604−10607.
(11) This mechanistic possibility has been proposed with diazo-
methane via an outer sphere attack or with an α-lithiated sulfone via
coordination/insertion, respectively: (a) Harrold, N. D.; Corcos, A.
R.; Hillhouse, G. L. Synthesis, structures, and catalytic reactivity of
bis(N-heterocyclic carbene) supported diphenyldiazomethane and 1-
azidoadamantane complexes of nickel. J. Organomet. Chem. 2016, 813,
46−54. (b) Gai, Y.; Julia, M.; Verpeaux, J.-N. Conversion of non-
activated alkenes into cyclopropanes with lithiated sulfones under
nickel catalysis. Bull. Soc. Chim. Fr. 1996, 133, 817−829.
(12) Concomitantly, the oxidation state of the transferred carbon
atom changes from −2 to −4 going from the ylidic carbon to the
carbenic carbon. Formally, this process can be regarded a reductive
cleavage of the C−N bond.
(13) (a) Tolman, C. A. Olefin Complexes of Nickel(0). III.
Formation Constants of (Olefin)bis(tri-o-tolyl phosphite)nickel
Complexes. J. Am. Chem. Soc. 1974, 96, 2780−2789. (b) The
analogous equilibrium constant for Ni(PPh3)3 and ethene has also
been measured and is comparable to the value with P(O-o-tolyl)3)
from ref 13a, K = 250 (ref 13a.) vs 300 (ref 13c): (c) Tolman, C. A.;
Seidel, W. C.; Gerlach, D. H. Triarylphosphine and Ethylene
Complexes of Zerovalent Nickel, Palladium, and Platinum. J. Am.
Chem. Soc. 1972, 94, 2669−2676.
(4) Kunzi, S. A.; Sarria Toro, J. M.; den Hartog, T.; Chen, P. Nickel-
̈
Catalyzed Cyclopropanation with NMe4OTf and nBuLi. Angew.
Chem., Int. Ed. 2015, 54, 10670−10674.
(5) We have made this observation for both the Ni-catalyzed
reaction in ref 4 as well as the uncatalyzed reaction in refs 10b and 15.
(6) All attempts to isolate a nickel carbene in analogy to Hillhouse’s
complexes derived from an ammonium ylide have failed so far. See:
(a) Mindiola, D. J.; Hillhouse, G. L. Synthesis, Structure, and
Reactions of a Three-Coordinate Nickel-Carbene Complex, {1,2-
Bis(di-tert-butylphosphino)ethane}Ni=CPh2. J. Am. Chem. Soc. 2002,
124, 9976−9977. (b) Iluc, V. M.; Hillhouse, G. L. Three-Coordinate
Nickel Carbene Complexes and Their One-Electron Oxidation
Products. J. Am. Chem. Soc. 2014, 136, 6479−6488.
(14) While the equilibrium constants measured in ref 13a were
determined under different conditions (benzene at room temperature
with P(O-o-tolyl)3) than our reaction conditions (THF at 0 °C with
PPh3), the qualitative trend should be the same. We opted for these
experimental values to already have a large library of alkenes at hand.
Additionally, we measured the binding constants for cyclooctene, 1-
octene, and norbornene with PPh3 (THF, room temperature) and
cyclooctene with P(O-o-tolyl)3 with a good agreement to Tolman’s
(7) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson,
G. A.; Nakatsuji, H.; Li, X.; Caricato, M.; Marenich, A.; Bloino, J.;
Janesko, B. G.; Gomperts, R.; Mennucci, B.; Hratchian, H. P.; Ortiz, J.
V.; Izmaylov, A. F.; Sonnenberg, J. L.; Williams-Young, D.; Ding, F.;
Lipparini, F.; Egidi, F.; Goings, J.; Peng, B.; Petrone, A.; Henderson,
T.; Ranasinghe, D.; Zakrzewski, V. G.; Gao, J.; Rega, N.; Zheng, G.;
Liang, W.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.;
Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.;
Throssell, K.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.;
Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V.
N.; Keith, T.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell,
A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Millam, J. M.;
Klene, M.; Adamo, C.; Cammi, R.; Ochterski, J. W.; Martin, R. L.;
Morokuma, K.; Farkas, O.; Foresman, J. B; Fox, D. J. Gaussian 09,
Revision D.01; Gaussian, Inc.: Wallingford, CT, 2016.
(15) Other (activated) alkenes with equilibrium constants K greater
than that of norbornene (see ref 13a) can already react with
[LiCH2N(CH3)3]OTf in an uncatalyzed addition-ring-closure se-
quence to give cyclopropanes (e.g., styrene (K = 10, ref 13a); see:
Sarria Toro, J. M.; den Hartog, T.; Chen, P. Cyclopropanation of
styrenes and stilbenes using lithiomethyl trimethylammonium triflate
as methylene donor. Chem. Commun. 2014, 50, 10608−10610.
(16) (a) Straub, B. Pd(0) Mechanism of Palladium-Catalyzed
Cyclopropanation of Alkenes by CH2N2: A DFT Study. J. Am. Chem.
Soc. 2002, 124, 14195−14201. (b) For a computational study for
cyclopropanation with a Ni carbene, see: Zhang, X.; Geng, Z.-Y.;
Wang, Y.-C.; Li, W.-Q.; Wang, Z.; Liu, F.-X. A theoretical study
nickel-catalyzed cyclopropanation reactions. Nickel(0) versus nickel-
(II). J. Mol. Struct.: THEOCHEM 2009, 893, 56−66.
(8) Anisimov, V.; Paneth, P. ISOEFF98. A program for studies of
isotope effects using Hessian modifications. J. Math. Chem. 1999, 26,
75−86.
(9) The ammonium ylide derived from deprotonating [BnNMe3]X
is known to undergo facile Stevens and Sommelet−Hauser rearrange-
ments and did so under our conditions (BuLi, THF, 0 °C, no [Ni] or
alkene present). (a) Stevens, T. S.; Creighton, E. M.; Gordon, A. B.;
MacNicol, M. CCCCXXIII.-Degradation of Quaternary Ammonium
Salts. Part I. J. Chem. Soc. 1928, 0, 3193−3197. (b) Puterbaugh, W.
H.; Hauser, C. R. Isolation of Intermediate Alkali Salt in ortho-
Substitution Rearrangement of Benzyltrimethylammonium Ion as
Benzophenone Adduct. J. Am. Chem. Soc. 1964, 86, 1105−1107.
(c) Lepley, A. R.; Becker, R. H. Quaternary benzylammonium ion
rearrangements with organolithium compounds-I: Simple tertiary
amines from the attack of N-butyl-lithium on benzyltrimethylammo-
nium iodide. Tetrahedron 1965, 21, 2365−2373.
(17) (a) Anciaux, A. J.; Hubert, A. J.; Noels, A. F.; Petiniot, N.;
́
Teyssie, P. Transition-Metal-Catalyzed Reactions of Diazo Com-
pounds. 1. Cyclopropanation of Double Bonds. J. Org. Chem. 1980,
45, 695−702. (b) Berthon-Gelloz, G.; Marchant, M.; Straub, B.;
Marko, I. E. Palladium-Catalyzed Cyclopropanation of Alkenyl Silanes
by Diazoalkanes: Evidence for a Pd0 Mechanism. Chem. - Eur. J. 2009,
15, 2923−2931.
(18) This sccenario is not unsimilar to the hydrogenation (under
low H2 pressure) of acetamidocinnamate with a cationic Rh(I)
catalyst, where the product ratio (enantiomeric excess) depends on
both the binding pre-equilibrium of the substrate and the subsequent
turnover-limiting step: Landis, C. R.; Halpern, J. Asymmetric
Hydrogenation of Methyl-(Z)-α-acetamidocinnamate Catalyzed by
(10) (a) On the basis of X-ray crytal structure of the complex
[(Cy3PCH(CH3)Ni(CO)3], it has been noted that the phosphonium
J
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