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(3) For selected examples of Cr-catalyzed carbometalation reactions
(9) For selected examples of Rh-catalyzed carbometalation reactions
between alkynes and organomagnesium reagents, see: (a) Murakami,
K.; Ohmiya, H.; Yorimitsu, H.; Oshima, K. Chromium-Catalyzed Ar-
ylmagnesiation of Alkynes. Org. Lett. 2007, 9, 1569-1571. (b) Yan, J.;
Yoshikai, N. Phenanthrene Synthesis via Chromium-Catalyzed Annu-
lation of 2-Biaryl Grignard Reagents and Alkynes. Org. Lett. 2017, 19,
6630-6633. (c) Yan, J.; Yoshikai, N. Chromium-catalyzed migratory
arylmagnesiation of unactivated alkynes. Org. Chem. Front. 2017, 4,
1972-1975.
(4) For the Mn-catalyzed addition of Grignard reagents to alkynes,
see: Yorimitsu, H.; Tang, J.; Okada, K.; Shinokubo, H.; Oshima, K.
Manganese-catalyzed Phenylation of Acetylenic Compounds with a
Phenyl Grignard Reagent. Chem. Lett. 1998, 27, 11-12.
between alkynes and arylboronic acids, see: (a) Hayashi, T.; Inoue, K.;
Taniguchi, N.; Ogasawara, M. Rhodium-Catalyzed Hydroarylation of
Alkynes with Arylboronic Acids:ꢀ 1,4-Shift of Rhodium from 2-Aryl-
1-alkenylrhodium to 2-Alkenylarylrhodium Intermediate. J. Am.
Chem. Soc. 2001, 123, 9918-9919. (b) Lautens, M.; Yoshida, M. Regi-
oselective Rhodium-Catalyzed Addition of Arylboronic Acids to Al-
kynes with a Pyridine-Substituted Water-Soluble Ligand. Org. Lett.
2002, 4, 123-125. (c) Zhang, W.; Liu, M.; Wu, H.; Ding, J.; Cheng, J.
Phosphine-free rhodium-catalyzed hydroarylation of diaryl acetylenes
with boronic acids. Tetrahedron Lett. 2008, 49, 5214–5216. (d) Schip-
per, D. J.; Hutchinson, M.; Fagnou K. Rhodium(III)-Catalyzed Inter-
molecular Hydroarylation of Alkynes. J. Am. Chem. Soc. 2010, 132,
6910-6911.
(10) For selected examples of Pd-catalyzed carbometalation reac-
tions with alkynes, see: (a) Oda, H.; Morishita, M.; Fugami, K.; Sano,
H.; Kosugi, M. A Novel Diarylation Reaction of Alkynes by Using Ar-
yltributylstannane in the Presence of Palladium Catalyst. Chem. Lett.
1996, 25, 811-812. (b) Oh, C. H.; Jung, H. H.; Kim, K. S.; Kim, N. The
Palladium‐Catalyzed Addition of Organoboronic Acids to Alkynes.
Angew. Chem., Int. Ed. 2003, 42, 805-808. (c) Cacchi, S.; Fabrizi, G.;
Goggiamani, A.; Persiani, D. Palladium-Catalyzed Hydroarylation of
Alkynes with Arenediazonium Salts. Org. Lett. 2008, 10, 1597-1600.
(d) Rao, S.; Joy, M. N.; Prabhu, K. R. Employing Water as the Hydride
Source in Synthesis: A Case Study of Diboron Mediated Alkyne Hy-
droarylation. J. Org. Chem. 2018, 83, 13707-13715.
(11) For a Co-catalyzed multicomponent coupling reaction which
employs carbon dioxide in conjunction with Zn as a reductant, see: (a)
Nogi, K.; Fujihara, T.; Terao, J.; Tsuji, Y. Carboxyzincation Employ-
ing Carbon Dioxide and Zinc Powder: Cobalt-Catalyzed Multicompo-
nent Coupling Reactions with Alkynes. J. Am. Chem. Soc. 2016, 138,
5547-5550. For examples of Ni-catalyzed reductive coupling reactions
which employ carbon dioxide, see: (b) Wang, X.; Liu, Y.; Martin, R.
Ni-Catalyzed Divergent Cyclization/Carboxylation of Unactivated Pri-
mary and Secondary Alkyl Halides with CO2. J. Am. Chem. Soc. 2015,
137, 6476-6479. (c) Gaydou, M.; Moragas, T.; Juliꢁ-Hernꢁndez, F.;
Martin, R. Site-Selective Catalytic Carboxylation of Unsaturated Hy-
drocarbons with CO2 and Water. J. Am. Chem. Soc. 2017, 139, 12161-
12164.
(12) For a Ni-catalyzed multicomponent coupling reaction which
employs aryl iodides in conjunction with Mn as a reductant, see: Dorn,
S. C. M.; Olsen, A. K.; Kelemen, R. E.; Shrestha, R.; Weix, D. J.
Nickel-catalyzed reductive arylation of activated alkynes with aryl io-
dides. Tetrahedron Lett. 2015, 56, 3365-3367. This reference also
serves as an example for Ni-catalyzed alkyne hydroarylation with syn
selectivity.
(13) For selected reviews discussing alkyne hydroarylation via tran-
sition-metal-catalyzed C–H activation, see: (a) Kakiuchi, F.; Murai, S.
Catalytic C-H/Olefin Coupling. Acc. Chem. Res. 2002, 35, 826-834. (b)
Gao, K.; Yoshikai, N. Low-Valent Cobalt Catalysis: New Opportuni-
ties for C−H Functionalization Acc. Chem. Res. 2014, 47, 1208−1219.
(c) Sambiago, C.; Schönbauer, D.; Blieck, R.; Dao-Huy, T.;
Pototschnig, G.; Schaaf, P.; Wiesinger, T.; Zia, M. F.; Wencel-Delord,
J.; Besset, T.; Maes, B. U. W.; Schnürch, M. A comprehensive over-
view of directing groups applied in metal-catalysed C–H functionaliza-
tion chemistry. Chem. Soc. Rev. 2018, 47, 6603-6743.
(14) For additional examples of Ni-catalyzed three-component cou-
plings reactions involving alkynes, see: (a) Ogata, K.; Atsuumi, Y.; Fu-
kuzawa, S.-i. Highly Chemoselective Nickel-Catalyzed Three-Compo-
nent Cross-Trimerization between Two Distinct Terminal Alkynes and
an Internal Alkyne. Org. Lett. 2011, 13, 122–125. (b) Li, Z.; García-
Domínguez, A.; Nevado, C. Nickel-Catalyzed Stereoselective Dicar-
bofunctionalization of Alkynes. Angew. Chem., Int. Ed. 2016, 55,
6938-6941. (c) Shimada, Y.; Ikeda, Z.; Matsubara, S. Preparation of
Organozinc Reagents via Catalyst Controlled Three-Component Cou-
pling between Alkyne, Iodoarene, and Bis(iodozincio)methane. Org.
Lett. 2017, 19, 3335–3337.
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(5) For selected examples of Fe-catalyzed carbometalation reactions
between alkynes and organolithium and/or organomagnesium reagents,
see: (a) Hojo, M.; Murakami, Y.; Aihara, H.; Sakuragi, R.; Baba, Y.;
Hosomi, A. Iron‐Catalyzed Regio‐ and Stereoselective Carbolithiation
of Alkynes. Angew. Chem., Int. Ed. 2001, 40, 621-623. (b) Shirakawa,
E.; Yamagami, T.; Kimura, T.; Yamaguchi, S.; Hayashi, T. Aryl-
magnesiation of Alkynes Catalyzed Cooperatively by Iron and Copper
Complexes. J. Am. Chem. Soc. 2005, 127, 17164-17165. (c) Zhang, D.;
Ready, J. M. Iron-Catalyzed Carbometalation of Propargylic and
Homopropargylic Alcohols. J. Am. Chem. Soc. 2006, 128, 15050-
15051. (d) Yamagami, T.; Shintani, R.; Shirakawa, E.; Hayashi, T.
Iron-Catalyzed Arylmagnesiation of Aryl(alkyl)acetylenes in the Pres-
ence of an N-Heterocyclic Carbene Ligand. Org. Lett. 2007, 9, 1045-
1048. (e) Shirakawa, E.; Masui, S.; Narui, R.; Watabe, R.; Ikeda, D.;
Hayashi, T. Iron-catalyzed aryl- and alkenyllithiation of alkynes and its
application to benzosilole synthesis. Chem. Commun. 2011, 47, 9714-
9716.
(6) For selected examples of Co-catalyzed carbometalation reactions
between alkynes and organozinc reagents, see: (a) Yasui, H.; Nishi-
kawa, T.; Yorimitsu, H.; Oshima, K. Cobalt-Catalyzed Allylzincations
of Internal Alkynes. Bull. Chem. Soc. Jpn. 2006, 79, 1271-1274. (b)
Murakami, K.; Yorimitsu, H.; Oshima, K. Cobalt-Catalyzed Arylzin-
cation of Alkynes. Org. Lett. 2009, 11, 2373-2375. (c) Corpet, M.; Gos-
mini, C. Cobalt-catalysed synthesis of highly substituted styrene deriv-
atives via arylzincation of alkynes. Chem. Commun. 2012, 48, 11561–
11563. (d) Wu, J.; Yoshikai, N. Cobalt‐Catalyzed Alkenylzincation of
Unfunctionalized Alkynes. Angew. Chem., Int. Ed. 2016, 55, 336-340.
(7) For selected examples of Ni-catalyzed carbometalation reactions
with alkynes, see: (a) Stüdemann, T.; Knochel, P. New Nickel‐Cata-
lyzed Carbozincation of Alkynes: A Short Synthesis of (Z)‐Tamoxifen.
Angew. Chem., Int. Ed. 1997, 36, 93-95. (b) Shirakawa, E.; Yamasaki,
K.; Yoshida, H.; Hiyama, T. Nickel-Catalyzed Carbostannylation of
Alkynes with Allyl-, Acyl-, and Alkynylstannanes:ꢀ Stereoselective
Synthesis of Trisubstituted Vinylstannanes. J. Am. Chem. Soc. 1999,
121, 10221-10222. (c) Suginome, M.; Shirakura, M.; Yamamoto, A.
Nickel-Catalyzed Addition of Alkynylboranes to Alkynes. J. Am.
Chem. Soc. 2006, 128, 14438-14439. (d) Murakami, K.; Ohmiya, H.;
Yorimitsu, H.; Oshima, K. Nickel-catalyzed Carbometalation Reac-
tions of [2-(1-Propynyl)phenyl]methanol with 1-Alkenylmagnesium
Reagents. Chem. Lett. 2007, 36, 1066-1067. (e) Xue, F.; Zhao, J.; Hor,
T. S. A. Ambient arylmagnesiation of alkynes catalysed by ligandless
nickel(II). Chem. Commun. 2013, 49, 10121-10123. (f) Xue, F.; Zhao,
J.; Hor, T. S. A.; Hayashi, T. Nickel-Catalyzed Three-Component
Domino Reactions of Aryl Grignard Reagents, Alkynes, and Aryl Hal-
ides Producing Tetrasubstituted Alkenes. J. Am. Chem. Soc. 2015, 137,
3189-3192.
(8) For selected examples of Cu-catalyzed carbometalation reactions
with alkynes, see: (a) Xie, M.; Huang, X. Carbomagnesiation of Acet-
ylenic Sulfones Catalyzed by CuCN and its Application in the Stere-
oselective Synthesis of Polysubstituted Vinyl Sulfones. Synlett 2003,
477-480. (b) Kortman, G. D.; Hull, K. L. Copper-Catalyzed Hydroary-
lation of Internal Alkynes: Highly Regio- and Diastereoselective Syn-
thesis of 1,1-Diaryl, Trisubstituted Olefins. ACS Catal. 2017, 7, 6220-
6224. (c) Nakamura, K.; Nishikata, T. Tandem Reactions Enable
Trans- and Cis-Hydro-Tertiary-Alkylations Catalyzed by a Copper
Salt. ACS. Catal. 2017, 7, 1049-1052.
(15) (a) Jia, C.; Piao, D.; Oyamada, J.; Lu, W.; Kitamura, T.; Fuji-
wara, Y. Efficient activation of aromatic C-H bonds for addition to C-
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