Page 5 of 6
ACS Catalysis
lecture). Angew. Chem. Int. Ed. 2011, 50, 6738ꢀ6764.
supported by bulky proazaphosphatrane ligands for
Stille crossꢀcoupling: coupling of aryl and vinyl
chlorides, room temperature coupling of aryl bromides,
coupling of aryl triflates, and synthesis of sterically
hindered biaryls. J. Am. Chem. Soc. 2004, 126, 16433ꢀ
16439.
Kosugi, M.; Tanji, T.; Tanaka, Y.; Yoshida, A.; Fugami,
K.; Kameyama, M.; Migita, T. Palladiumꢀcatalyzed
reaction of 1ꢀazaꢀ5ꢀgermaꢀ5ꢀorganobicyclo [3.3. 3]
undecane with aryl bromide. J. Organomet. Chem.
1996, 508, 255ꢀ257.
1
2
3
4
5
6
7
8
9
(b) Knochel, P.; Singer, R. D. Preparation and reactions
of polyfunctional organozinc reagents in organic
synthesis. Chem. Rev. 1993, 93, 2117ꢀ2188.
(
6)
For recent reviews and selected examples: (a) Knappke,
C. E. I.; Jacobi von Wangelin, A. 35 years of palladiumꢀ
catalyzed crossꢀcoupling with Grignard reagents: how
far have we come?. Chem. Soc. Rev. 2011, 40, 4948ꢀ
4962. (b) Tamao, K.; Sumitani, K.; Kumada, M.
Selective carbonꢀcarbon bond formation by crossꢀ
coupling of Grignard reagents with organic halides.
Catalysis by nickelꢀphosphine complexes. J. Am. Chem.
Soc. 1972, 94, 4374ꢀ4376.
(a) Giannerini, M.; FananasꢀMastral, M.; Feringa, B. L.
Direct catalytic crossꢀcoupling of organolithium
compounds. Nat. Chem. 2013, 5, 667ꢀ672. (b)
Giannerini, M.; Hornillos, V.; Vila, C.; Fananasꢀ
Mastral, M.; Feringa, B. L. Hindered Aryllithium
Reagents as Partners in Palladium‐ Catalyzed Cross‐
Coupling: Synthesis of Tri‐ and Tetra‐ ortho‐
Substituted Biaryls under Ambient Conditions. Angew.
Chem. Int. Ed. 2013, 52, 13329ꢀ13333.
(a) Blumke, T.; Chen, Y. H.; Peng, Z. H.; Knochel, P.
Preparation of functionalized organoaluminiums by
direct insertion of aluminium to unsaturated halides.
Nat. Chem. 2010, 2, 313ꢀ318. (b) Minami, H.; Saito, T.;
Wang, C.; Uchiyama, M. Organoaluminum‐ Mediated
Direct Cross‐ Coupling Reactions. Angew. Chem. Int.
Ed. 2015, 54, 4665ꢀ4668.
(a) Han, J. W.; Tokunaga, N.; Hayashi, T. Palladiumꢀor
nickelꢀcatalyzed crossꢀcoupling of organotitanium
reagents with aryl triflates and halides. Synlett 2002,
(15)
(16)
(17)
Faller, J. W.; Kultyshev, R. G. Palladiumꢀcatalyzed
crossꢀcoupling reactions of allyl, phenyl, alkenyl, and
alkynyl germatranes with aryl iodides. Organometallics
2002, 21, 5911ꢀ5918.
1
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2
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4
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4
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5
5
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Seemingly
expensive
inorganic
Geꢀcontaining
chemicals, which mainly apply in materials industry,
can be credited to their high purity. In fact, in this work,
all Geꢀcontaining reagents can be synthesized from
industry crude GeO (roughly 1 $/g).
2
(18)
(19)
Jung, M. E.; Piizzi, G. Gemꢀdisubstituent effect:
theoretical basis and synthetic applications. Chem. Rev.
2005, 105, 1735ꢀ1766.
Enokido, T.; Fugami, K.; Endo, M.; Kameyama, M.;
Kosugi, M. Palladium‐ Catalyzed Cross‐ Coupling
Reaction by Means of Organogermanium Trichlorides.
Adv. Synth. Catal. 2004, 346, 1685ꢀ1688.
Endo, M.; Fugami, K.; Enokido, T.; Sano, H.; Kosugi,
M. Palladium‐ Catalyzed Cross‐ Coupling Reaction
Using Arylgermanium Sesquioxide. Adv. Synth. Catal.
2007, 349, 1025ꢀ1027.
Blackaby, W. P.; Atack, J. R.; Bromidge, F.; Castro, J.
L.; Goodacre, S. C.; Hallett, D. J.; Lewis, R. T.;
Marshall, G. R.; Pike, A.; Smith, A. J.; Street, L. J.;
Tattersall, D. F. D.; Wafford, K. A. Imidazo [1,2ꢀa]
pyrimidines as functionally selective GABAA ligands.
Bioorg. Med. Chem. Lett. 2006, 16, 1175ꢀ1179.
(a) Lehmann, J. W.; Blair, D. J.; Burke, M. D. Towards
the generalized iterative synthesis of small molecules.
Nat. Rev. Chem. 2018, 2, 0115. (b) Dobrounig, P.;
Trobe, M.; Breinbauer, R. Sequential and iterative Pdꢀ
catalyzed crossꢀcoupling reactions in organic synthesis.
Monatsh. Chem. 2017, 148, 3ꢀ35.
(8)
(20)
(21)
(
9)
2
002, 0871ꢀ0874. (b) Lee, H. W.; Lam, F. L.; So, C. M.;
Lau, C. P.; Chan, A. S.; Kwong, F. Y. Palladium‐
Catalyzed Cross‐ Coupling of Aryl Halides Using
Organotitanium Nucleophiles. Angew. Chem. Int. Ed.
2
009, 48, 7436ꢀ7439. (c) Knochel, P.; Manolikakes, G.;
Dastbaravardeh, N. Nickelꢀcatalyzed crossꢀcoupling
reactions of aryltitanium (IV) alkoxides with aryl
halides. Synlett 2007, 2007, 2077ꢀ2080.
Goossen, L. J.; Deng, G.; Levy, L. M. Synthesis of
biaryls via catalytic decarboxylative coupling. Science
(22)
(
10)
11)
2
006, 313, 662ꢀ664.
(
Spivey, A. C.; Gripton, C. J. G.; Hannah, J. P. Recent
advances in group 14 crossꢀcoupling: Si and Geꢀbased
alternatives to the Stille reaction. Curr. Org. Synth.
(23)
(24)
Li, J.; Grillo, A. S.; Burke, M. D. From synthesis to
function
via
iterative
assembly
of
Nꢀ
methyliminodiacetic acid boronate building blocks. Acc.
Chem. Res. 2015, 48, 2297ꢀ2307.
2
004, 1, 211ꢀ226.
(
12)
Karni, M.; Apeloig, Y.; Kapp, J.; Schleyer, P. v. R.
Theoretical aspects of compounds containing Si, Ge, Sn
and Pb. The Chemistry of Organic Silicon Compounds
(a) Yoshimura, A.; Zhdankin, V. V. Advances in
synthetic applications of hypervalent iodine compounds.
Chem. Rev. 2016, 116, 3328ꢀ3435. (b) Hickman, A. J.;
Sanford, M. S. Highꢀvalent organometallic copper and
palladium in catalysis. Nature 2012, 484, 177ꢀ185.
(a) Phipps, R. J.; Grimster, N. P.; Gaunt, M. J. Cu(II)ꢀ
catalyzed direct and siteꢀselective arylation of indoles
under mild conditions. J. Am. Chem. Soc. 2008, 130,
8172ꢀ8174. (b) Pitts, A. K.; O'Hara, F.; Snell, R. H.;
Gaunt, M. J. A Concise and Scalable Strategy for the
Total Synthesis of Dictyodendrin B Based on Sequential
CꢀH Functionalization. Angew. Chem. Int. Ed. 2015, 54,
5451ꢀ5455.
2
001, 3, 1ꢀ163.
(13)
The abundance of Ge in earth’s crust is only slightly
lower than Sn (1.8 ppm vs 2.2 ppm), See: (a) Barbalace,
Kenneth. Periodic Table of Elements. Environmental
Chemistry.com. (b) Abundance in Earth's Crust.
WebElements.com. (c) It's Elemental — The Periodic
Table of Elements. Jefferson Lab.
(a) Verkade, J. G. Atranes: new examples with
unexpected properties. Acc. Chem. Res. 1993, 26, 483ꢀ
489. (b) Su, W.; Urgaonkar, S.; McLaughlin, P. A.;
Verkade, J. G. Highly active palladium catalysts
(25)
(
14)
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