Journal of the American Chemical Society
Page 4 of 5
Dynamic Phosphorous Triamide. J. Am. Chem. Soc. 2014, 136, 17634-
ASSOCIATED CONTENT
17644. (d) Lin, Y.-C.; Hatzakis, E.; McCarthy, S. M.; Reichl, K. D.; Lai,
T.-Y.; Yennawar, H. P.; Radosevich, A. T., P–N Cooperative Borane
Activation and Catalytic Hydroboration by a Distorted Phosphorous
Triamide Platform. J. Am. Chem. Soc. 2017, 139, 6008-6016. (e) Nykaza,
T. V.; Cooper, J. C.; Li, G.; Mahieu, N.; Ramirez, A.; Luzung, M. R.;
Radosevich, A. T., Intermolecular Reductive C–N Cross Coupling of
Nitroarenes and Boronic Acids by PIII/PV═O Catalysis. J. Am. Chem. Soc.
2018, 140, 15200-15205. (f) Reichl, K. D.; Dunn, N. L.; Fastuca, N. J.;
Radosevich, A. T., Biphilic Organophosphorus Catalysis: Regioselective
Reductive Transposition of Allylic Bromides via PIII/PV Redox Cycling. J.
Am. Chem. Soc. 2015, 137, 5292-5295. (g) Nykaza, T. V.; Harrison, T. S.;
Ghosh, A.; Putnik, R. A.; Radosevich, A. T., A Biphilic Phosphetane
Catalyzes N–N Bond-Forming Cadogan Heterocyclization via PIII/PV═O
Redox Cycling. J. Am. Chem. Soc. 2017, 139, 6839-6842. (h) Zhao, W.;
Yan, P. K.; Radosevich, A. T., A Phosphetane Catalyzes Deoxygenative
Condensation of α-Keto Esters and Carboxylic Acids via PIII/PV═O Redox
Cycling. J. Am. Chem. Soc. 2015, 137, 616-619. (i) Nykaza, T. V.;
Ramirez, A.; Harrison, T. S.; Luzung, M. R.; Radosevich, A. T., Biphilic
1
2
3
4
5
6
7
8
Supporting Information. Experimental procedures and analyti-
cal data (1H and 13C NMR, HRMS) for all new compounds. This
material is available free of charge via the internet at
AUTHOR INFORMATION
Corresponding Authors
Notes
†
9
F.W. and O.P. contributed equally.
The authors declare no competing financial interest.
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
ACKNOWLEDGMENT
Financial support for this work was provided by Max-Planck-
Gesellschaft, Max-Planck-Institut für Kohlenforschung and Fonds
der Chemischen Industrie (FCI-VCI). We thank Prof. Dr. A.
Fürstner for insightful discussions and generous support. O.P.
thanks the Alexander von Humboldt foundation for a post-
doctoral research fellowship.
Organophosphorus-Catalyzed Intramolecular
Csp2–H
Amination:
Evidence for a Nitrenoid in Catalytic Cadogan Cyclizations. J. Am. Chem.
Soc. 2018, 140, 3103-3113.
(8) Arduengo, A. J.; Stewart, C. A., Low coordinate hypervalent
phosphorus. Chem. Rev. 1994, 94, 1215-1237.
(9) de Marcillac, P.; Coron, N.; Dambier, G.; Leblanc, J.; Moalic, J.-P.,
Experimental detection of α-particles from the radioactive decay of natural
bismuth. Nature 2003, 422, 876-878.
(10) (a) Mehring, M., From molecules to bismuth oxide-based materials:
Potential homo- and heterometallic precursors and model compounds.
Coord. Chem. Rev. 2007, 251, 974-1006. (b) Briand, G. G.; Burford, N.,
Coordination complexes of bismuth(III) involving organic ligands with
pnictogen or chalcogen donors. In Adv. Inorg. Chem., Academic Press:
2000; Vol. 50, pp 285-357.
REFERENCES
(1) (a) Hartwig, J. F., Organotransition metal chemistry: from bonding to
catalysis. University Science Books: Mill Valley, California, 2010. (b)
Crabtree, R. H., The Organometallic Chemistry of the Transition Metals.
John Wiley & Sons: Hoboken, New Jersey, 2005. (c) de Meijere, A.;
Diederich, F., Metal-Catalyzed Cross-Coupling Reactions. WILEY‐VCH
Verlag GmbH & Co. KGaA Mörlenbach, Germany, 2004.
(2) (a) Zweig, J. E.; Kim, D. E.; Newhouse, T. R., Methods Utilizing
First-Row Transition Metals in Natural Product Total Synthesis. Chem.
Rev. 2017, 117, 11680-11752. (b) Su, B.; Cao, Z.-C.; Shi, Z.-J.,
Exploration of Earth-Abundant Transition Metals (Fe, Co, and Ni) as
Catalysts in Unreactive Chemical Bond Activations. Acc. Chem. Res.
2015, 48, 886-896.
(3) (a) Bauer, H.; Alonso, M.; Färber, C.; Elsen, H.; Pahl, J.; Causero, A.;
Ballmann, G.; De Proft, F.; Harder, S., Imine hydrogenation with simple
alkaline earth metal catalysts. Nat. Catal. 2018, 1, 40-47. (b) Hill, M. S.;
Liptrot, D. J.; Weetman, C., Alkaline earths as main group reagents in
molecular catalysis. Chem. Soc. Rev. 2016, 45, 972-988. (c) Kobayashi,
S.; Yamashita, Y., Alkaline Earth Metal Catalysts for Asymmetric
Reactions. Acc. Chem. Res. 2011, 44, 58-71.
(4) (a) Weetman, C.; Inoue, S., The Road Travelled: After Main-Group
Elements as Transition Metals. ChemCatChem 2018, 10, 4213-4228. (b)
Chu, T.; Nikonov, G. I., Oxidative Addition and Reductive Elimination at
Main-Group Element Centers. Chem. Rev. 2018, 118, 3608-3680. (c)
Yadav, S.; Saha, S.; Sen, S. S., Compounds with Low-Valent p-Block
Elements for Small Molecule Activation and Catalysis. ChemCatChem
2015, 8, 486-501. (d) Raţ, C. I.; Soran, A.; Varga, R. A.; Silvestru, C., C–
(11) Mohan, R., Green bismuth. Nat. Chem. 2010, 2, 336.
(12) (a) Leonard, N. M.; Wieland, L. C.; Mohan, R. S., Applications of
bismuth(III) compounds in organic synthesis. Tetrahedron 2002, 58,
8373-8397. (b) Ollevier, T. Bismuth-Mediated Organic Reactions,
Springer, Berlin, Heidelberg, 2012; (c) Ruimao, H., Recent Advances in
Bismuth-Catalyzed Organic Synthesis. Curr. Org. Synth. 2008, 5, 1-27.
(13) (a) Collins, L. R.; van Gastel, M.; Neese, F.; Fürstner, A., Enhanced
Electrophilicity of Heterobimetallic Bi–Rh Paddlewheel Carbene
Complexes:
A
Combined Experimental,
Spectroscopic, and
Computational Study. J. Am. Chem. Soc. 2018, 140, 13042-13055. (b)
Ren, Z.; Sunderland, T. L.; Tortoreto, C.; Yang, T.; Berry, J. F.; Musaev,
D. G.; Davies, H. M. L., Comparison of Reactivity and Enantioselectivity
between Chiral Bimetallic Catalysts: Bismuth–Rhodium- and Dirhodium-
Catalyzed Carbene Chemistry. ACS Catal. 2018, 8, 10676-10682.
(14) (a) Ritschel, B.; Poater, J.; Dengel, H.; Bickelhaupt, F. M.;
Lichtenberg, C., Double C-H Activation of a Masked Cationic Bismuth
Amide. Angew. Chem. Int. Ed. 2018, 57, 3825-3829. (b) Casely, I. J.;
Ziller, J. W.; Fang, M.; Furche, F.; Evans, W. J., Facile Bismuth−Oxygen
Bond Cleavage, C−H Activation, and Formation of a Monodentate
Carbon-Bound Oxyaryl Dianion, (C6H2tBu2-3,5-O-4)2−. J. Am. Chem. Soc.
2011, 133, 5244-5247. (c) Kindra, D. R.; Casely, I. J.; Fieser, M. E.;
Ziller, J. W.; Furche, F.; Evans, W. J., Insertion of CO2 and COS into Bi–
C Bonds: Reactivity of a Bismuth NCN Pincer Complex of an Oxyaryl
Dianionic Ligand, [2,6-(Me2NCH2)2C6H3]Bi(C6H2tBu2O). J. Am. Chem.
Soc. 2013, 135, 7777-7787. (d) Nekoueishahraki, B.; Sarish, S. P.;
Roesky, H. W.; Stern, D.; Schulzke, C.; Stalke, D., Addition of
Dimethylaminobismuth to Aldehydes, Ketones, Alkenes, and Alkynes.
Angew. Chem. Int. Ed. 2009, 48, 4517-4520.
H
Bond Activation Mediated by Inorganic and Organometallic
Compounds of Main Group Metals. Adv. Organomet. Chem. 2018, 70,
233-311; (e) Frey, G. D; Lavallo, V.; Donnadieu, B.; Schoeller, W. W.;
Bertrand, Facile Splitting of Hydrogen and Ammonia by Nucelophilic
Activation at a Single Carbon Center. Science, 2007, 316, 439.
(5) (a) Hounjet, L. J.; Stephan, D. W., Hydrogenation by Frustrated Lewis
Pairs: Main Group Alternatives to Transition Metal Catalysts? Org.
Process Res. Dev. 2014, 18, 385-391. (b) Stephan, D. W., Frustrated
Lewis Pairs: From Concept to Catalysis. Acc. Chem. Res. 2015, 48, 306-
316. (c) Stephan, D. W.; Erker, G., Frustrated Lewis Pair Chemistry:
Development and Perspectives. Angew. Chem. Int. Ed. 2015, 54, 6400-
6441.
(6) (a) Power, P. P. Main Group Elements as Transition Metals, Nature,
2010, 463, 171-177; (b) Melen, R. L. Frontiers in Molecular p-block
chemistry: From Structure to Reactivity. Science 2019, 363, 479-484.
(7) (a) Dunn, N. L.; Ha, M.; Radosevich, A. T., Main Group Redox
Catalysis: Reversible PIII/PV Redox Cycling at a Phosphorus Platform. J.
Am. Chem. Soc. 2012, 134, 11330-11333. (b) McCarthy, S. M.; Lin, Y.-
C.; Devarajan, D.; Chang, J. W.; Yennawar, H. P.; Rioux, R. M.; Ess, D.
H.; Radosevich, A. T., Intermolecular N–H Oxidative Addition of
Ammonia, Alkylamines, and Arylamines to a Planar σ3-Phosphorus
Compound via an Entropy-Controlled Electrophilic Mechanism. J. Am.
Chem. Soc. 2014, 136, 4640-4650. (c) Zhao, W.; McCarthy, S. M.; Lai, T.
Y.; Yennawar, H. P.; Radosevich, A. T., Reversible Intermolecular E–H
(15) (a) Lichtenberg, C., Well-Defined, Mononuclear BiI and BiII
Compounds: Towards Transition-Metal-Like Behavior. Angew. Chem. Int.
Ed. 2016, 55, 484-486. (b) Ellis, B. D.; Macdonald, C. L. B., Stable
compounds containing heavier group 15 elements in the +1 oxidation
state. Coord. Chem. Rev. 2007, 251, 936-973.
(16) (a) Šimon, P.; de Proft, F.; Jambor, R.; Růžička, A.; Dostál, L.,
Monomeric Organoantimony(I) and Organobismuth(I) Compounds
Stabilized by an NCN Chelating Ligand: Syntheses and Structures.
Angew. Chem. Int. Ed. 2010, 49, 5468-5471. (b) Vránová, I.; Alonso, M.;
Lo, R.; Sedlák, R.; Jambor, R.; Růžička, A.; Proft, F. D.; Hobza, P.;
Dostál, L., From Dibismuthenes to Three- and Two-Coordinated
Bismuthinidenes by Fine Ligand Tuning: Evidence for Aromatic BiC3N
Rings through a Combined Experimental and Theoretical Study. Chem.
Eur. J. 2015, 21, 16917-16928. (c) Vránová, I.; Dušková, T.; Erben, M.;
Oxidative Addition to
a Geometrically Deformed and Structurally
ACS Paragon Plus Environment