Journal of the American Chemical Society
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dialkoxycarbenes: Control of the stereoselectivity and a mechanistic
portrait" J. Am. Chem. Soc. 2012, 134, 5938-5953.
NSF (CHE-1625543). We thank Matthias Zeller for assistance with
X-ray crystallography and Dr. Houng Kang for experimental
assistance. C.U. acknowledges support from a Camille Dreyfus
Teacher–Scholar award and a Lilly Grantee award.
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3
4
5
6
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(6) Examples of diene carbonylation reactions: (a) Eaton, B. E.;
Rollman, B.; Kaduk, J. A. "The first catalytic iron-mediated [4 + 1]
cyclopentenone assembly: Stereoselective synthesis of 2,5-
dialkylidenecyclo-3-pentenones" J. Am. Chem. Soc. 1992, 114, 6245-
6246; (b) Sigman, M. S.; Eaton, B. E. "Catalytic iron-mediated [4 + 1]
cycloaddition of diallenes with carbon monoxide" J. Am. Chem. Soc.
1996, 118, 11783-11788; (c) Murakami, M.; Itami, K.; Ito, Y. "A study
on rhodium – vinylallene complexes leading to a new reaction,
rhodium‐catalyzed carbonylative [4 + 1]cycloaddition" Angew. Chem.,
Int. Ed. 1996, 34, 2691-2694; (d) Murakami, M.; Itami, K.; Ito, Y.
"Rhodium-catalyzed asymmetric [4 + 1] cycloaddition" J. Am. Chem.
Soc. 1997, 119, 2950-2951; (e) Murakami, M.; Itami, K.; Ito, Y.
"Catalytic asymmetric [4 + 1] cycloaddition of vinylallenes with carbon
monoxide: Reversal of the induced chirality by the choice of metal" J.
Am. Chem. Soc. 1999, 121, 4130-4135.
REFERENCES
(1) Yoon, T. P.; Jacobsen, E. N. "Privileged chiral catalysts" Science
2003, 299, 1691-1693.
(2) (a) Ghosh, A. K.; Mathivanan, P.; Cappiello, J. "C2-symmetric
chiral bis(oxazoline)–metal complexes in catalytic asymmetric
synthesis" Tetrahedron: Asymmetry 1998, 9, 1-45; (b) Johnson, J. S.;
Evans, D. A. "Chiral bis(oxazoline) copper(II) complexes:ꢀ Versatile
catalysts for enantioselective cycloaddition, aldol, michael, and
carbonyl ene reactions" Acc. Chem. Res. 2000, 33, 325-335; (c) Fache,
F.; Schulz, E.; Tommasino, M. L.; Lemaire, M. "Nitrogen-containing
ligands for asymmetric homogeneous and heterogeneous catalysis"
Chem. Rev. 2000, 100, 2159-2232; (d) Desimoni, G.; Faita, G.;
Quadrelli, P. "Pyridine-2,6-bis(oxazolines), helpful ligands for
asymmetric catalysts" Chem. Rev. 2003, 103, 3119-3154; (e) Desimoni,
G.; Faita, G.; Jørgensen, K. A. "C2-symmetric chiral bis(oxazoline)
ligands in asymmetric catalysis" Chem. Rev. 2006, 106, 3561-3651; (f)
Rasappan, R.; Laventine, D.; Reiser, O. "Metal-bis(oxazoline)
complexes: From coordination chemistry to asymmetric catalysis"
Coord. Chem. Rev. 2008, 252, 702-714; (g) Babu, S. A.; Krishnan, K.
K.; Ujwaldev, S. M.; Anilkumar, G. "Applications of pybox complexes
in asymmetric catalysis" Asian J. Org. Chem. 2018, 7, 1033-1053.
(3) (a) Doyle, M. P. "Perspective on dirhodium carboxamidates as
catalysts" J. Org. Chem. 2006, 71, 9253-9260; (b) Davies, H. M. L.;
Manning, J. R. "Catalytic C-H functionalization by metal carbenoid
and nitrenoid insertion" Nature 2008, 451, 417-424; (c) Davies, H. M.
L.; Morton, D. "Guiding principles for site selective and stereoselective
intermolecular C-H functionalization by donor/acceptor rhodium
carbenes" Chem. Soc. Rev. 2011, 40, 1857-1869; (d) Paton, R. S.;
Brown, J. M. "Dinuclear palladium complexes—precursors or
catalysts?" Angew. Chem., Int. Ed. 2012, 51, 10448-10450; (e)
Kornecki, K. P.; Berry, J. F.; Powers, D. C.; Ritter, T. In Prog. Inorg.
Chem.; Karlin, K. D., Ed.; John Wiley & Sons, Inc.: Hoboken, New
Jersey, 2014; Vol. 58, p 225-302; (f) Mankad, N. P. "Selectivity effects
in bimetallic catalysis" Chem.-Eur. J. 2016, 22, 5822-5829; (g) Powers,
I. G.; Uyeda, C. "Metal-metal bonds in catalysis" ACS Catalysis 2017,
7, 936-958; (h) Farley, C. M.; Uyeda, C. "Organic reactions enabled by
catalytically active metal-metal bonds" Trends in Chem. 2019, 1, 497-
509.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(7) Zhou, Y.-Y.; Uyeda, C. "Catalytic reductive [4 + 1]-
cycloadditions of vinylidenes and dienes" Science 2019, 363, 857-862.
(8) Cramer, N.; Braconi, E. "A chiral naphthyridine diimine ligand
platform
enables
nickel-catalyzed
asymmetric
alkylidenecyclopropanations" Angew. Chem., Int. Ed., 2020, 59, 1-6.
(9) (a) Fahrni, C. J. "Allylic oxidation catalyzed by chiral dinuclear
copper complexes" Tetrahedron 1998, 54, 5465-5470; (b) Fahrni, C. J.;
Pfaltz, A. "Synthesis of chiral C2-symmetric binucleating ligands"
Helv. Chim. Acta 1998, 81, 491-506; (c) Fahrni, C. J.; Pfaltz, A.;
Neuburger, M.; Zehnder, M. "Structure and properties of transition-
metal complexes with chiral C2-symmetric binucleating ligands" Helv.
Chim. Acta 1998, 81, 507-524.
(10) Zhou, Y.-Y.; Hartline, D. R.; Steiman, T. J.; Fanwick, P. E.;
Uyeda, C. "Dinuclear nickel complexes in five states of oxidation using
a redox-active ligand" Inorg. Chem. 2014, 53, 11770-11777.
(11) (a) Dible, B. R.; Sigman, M. S.; Arif, A. M. "Oxygen-induced
ligand dehydrogenation of a planar bis-μ-chloronickel(I) dimer
featuring an NHC ligand" Inorg. Chem. 2005, 44, 3774-3776; (b) Keen,
A. L.; Johnson, S. A. "Nickel(0)-catalyzed isomerization of an aryne
complex:ꢀ Formation of a dinuclear Ni(I) complex via C−H rather than
C−F bond activation" J. Am. Chem. Soc. 2006, 128, 1806-1807; (c)
Velian, A.; Lin, S.; Miller, A. J. M.; Day, M. W.; Agapie, T. "Synthesis
and C−C coupling reactivity of a dinuclear NiI−NiI complex supported
by a terphenyl diphosphine" J. Am. Chem. Soc. 2010, 132, 6296-6297;
(d) Beck, R.; Johnson, S. A. "Dinuclear Ni(I)—Ni(I) complexes with
syn-facial bridging ligands from Ni(I) precursors or Ni(II)/Ni(0)
comproportionation" Organometallics 2013, 32, 2944-2951; (e)
Cornella, J.; Gómez-Bengoa, E.; Martin, R. "Combined experimental
and theoretical study on the reductive cleavage of inert C–O bonds with
silanes: Ruling out a classical Ni(0)/Ni(II) catalytic couple and
evidence for Ni(I) intermediates" J. Am. Chem. Soc. 2013, 135, 1997-
2009; (f) Wu, J.; Nova, A.; Balcells, D.; Brudvig, G. W.; Dai, W.;
Guard, L. M.; Hazari, N.; Lin, P. H.; Pokhrel, R.; Takase, M. K. "Nickel
(I) monomers and dimers with cyclopentadienyl and indenyl ligands"
Chem.-Eur. J. 2014, 20, 5327-5337.
(4) (a) Turkenburg, L. A. M.; de Worlf, W. H.; Bickelhaupt, F. "1,4-
addition of dichlorocarbene to 1,2-bismethylenecycloheptane"
Tetrahedron Lett. 1982, 23, 769-770; (b) Sugita, H.; Mizuno, K.; Mori,
T.; Isagawa, K.; Otsuji, Y. "Unusual mode of addition of
1,2‐alkadienylidene carbenes to 1,3‐dienes: 1,4 addition to rigid and
flexible 1,3‐dienes" Angew. Chem., Int. Ed. 1991, 30, 984-986; (c)
Boisvert, L.; Beaumier, F.; Spino, C. "Evidence for a concerted [4 + 1]-
cycloaddition between electron-rich carbenes and electron-deficient
dienes" Org. Lett. 2007, 9, 5361-5363.
(12) (a) Knijnenburg, Q.; Hetterscheid, D.; Kooistra, T. M.;
(5) Examples of tandem cyclopropanation/1,3-rearrangement
reactions: (a) Danheiser, R. L.; Martinez-Davila, C.; Auchus, R. J.;
Kadonaga, J. T. "Stereoselective synthesis of cyclopentene derivatives
from 1,3-dienes" J. Am. Chem. Soc. 1981, 103, 2443-2446; (b)
Hudlicky, T.; Koszyk, F. F.; Kutchan, T. M.; Sheth, J. P. "Cyclopentene
annulation via intramolecular addition of diazoketones to 1,3-dienes.
Applications to the synthesis of cyclopentanoid terpenes" J. Org.
Chem. 1980, 45, 5020-5027; (c) Danheiser, R. L.; Bronson, J. J.;
Okano, K. "Carbanion-accelerated vinylcyclopropane rearrangement.
Application in a general, stereocontrolled annulation approach to
cyclopentene derivatives" J. Am. Chem. Soc. 1985, 107, 4579-4581; (d)
Coscia, R. W.; Lambert, T. H. "Development of a formal [4 + 1]
cycloaddition: Pd(OAc)2-catalyzed intramolecular cyclopropanation of
Budzelaar,
Peter H.
M.
"The
electronic
structure
of
(diiminopyridine)cobalt(I) complexes" Eur. J. Inorg. Chem. 2004,
2004, 1204-1211; (b) Jones, G. D.; Martin, J. L.; McFarland, C.; Allen,
O. R.; Hall, R. E.; Haley, A. D.; Brandon, R. J.; Konovalova, T.;
Desrochers, P. J.; Pulay, P.; Vicic, D. A. "Ligand redox effects in the
synthesis, electronic structure, and reactivity of an alkyl−alkyl cross-
coupling catalyst" J. Am. Chem. Soc. 2006, 128, 13175-13183; (c) Bart,
S. C.; Chłopek, K.; Bill, E.; Bouwkamp, M. W.; Lobkovsky, E.; Neese,
F.; Wieghardt, K.; Chirik, P. J. "Electronic structure of
bis(imino)pyridine iron dichloride, monochloride, and neutral ligand
complexes:ꢀ A combined structural, spectroscopic, and computational
study" J. Am. Chem. Soc. 2006, 128, 13901-13912; (d) Bowman, A. C.;
Milsmann, C.; Hojilla Atienza, C. C.; Lobkovsky, E.; Wieghardt, K.;
Chirik, P. J. "Synthesis and molecular and electronic structures of
reduced bis(imino)pyridine cobalt dinitrogen complexes: Ligand
versus metal reduction" J. Am. Chem. Soc. 2010, 132, 1676-1684.
(13) Schley, N. D.; Fu, G. C. "Nickel-catalyzed negishi arylations of
1,3-dienyl
β-keto
esters
and
MgI2-promoted
vinylcyclopropane−cyclopentene rearrangement" J. Am. Chem. Soc.
2009, 131, 2496-2498; (e) Beaumier, F.; Dupuis, M.; Spino, C.;
Legault, C. Y. "Formal intramolecular (4 + 1)-cycloaddition of
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