9
1.4 Development and Outlook
Currently, tremendous amount of excellent work is still publishing on oxidative
cross-couplings between two different nucleophiles especially those C-H nucleophiles. However, challenges still remain in this research area, such as the selective
control of the reactive site of hydrocarbons. Moreover, understandings of this concept are still superficial and incomplete, and the mechanistic study in this area is
still in its primary stage. Along with the development of transition metal-catalyzed
oxidative cross-couplings, especially of those none noble transition metal catalysis
system, radical process becomes dominating in the research area. More and more
examples will be developed in the future. And there are still many unexplored
methods and unknown insightful mechanism left. Therefore, chances and challenges are still remaining, such as finding milder reaction conditions and proper
ways to control the reactivity and chemoselectivity of radical species. Thus developing new, greener, and more efficient radical oxidative cross-couplings is still an
urgent work in the future. Furthermore, external oxidant-free oxidative cross-coupling between two C-H with the release of hydrogen gas would be a very promising
direction for oxidative cross-couplings. This area is more atomic economy and consistent with sustainable development, with no wasteful by-products or oxidation
side reactions, and the environment is sustainable. It holds significant potential for
the applications to a series of organic reactions, and scientists paid more and more
attention on this field.
References
1. Baba S, Negishi E (1976) A novel stereospecific alkenyl-alkenyl cross-coupling by a palladium- or nickel-catalyzed reaction of alkenylalanes with alkenyl halides. J Am Chem Soc
98:6729–6731. https://doi.org/10.1021/ja00437a067
2. Ghose R, Hwang HT, Varma A (2014) Oxidative coupling of methane using catalysts synthesized by solution combustion method: catalyst optimization and kinetic studies. Appl Catal A
472:39–46. https://doi.org/10.1016/j.apcata.2013.12.004
3. Glaser C (1869) Beiträge zur Kenntniss des Acetenylbenzols. Ber Dtsch Chem Ges 2:422–
424. https://doi.org/10.1002/cber.186900201183
4. Guram AS, Rennels RA, Buchwald SL (1995) A simple catalytic method for the conversion
of aryl bromides to Arylamines. Angew Chem Int Ed 34:1348–1350. https://doi.org/10.1002/
anie.199513481
5. Hatanaka Y, Hiyama T (1988) Cross-coupling of organosilanes with organic halides mediated
by a palladium catalyst and tris(diethylamino)sulfonium difluorotrimethylsilicate. J Org Chem
53:918–920. https://doi.org/10.1021/jo00239a056
6. Heck RF, Nolley JP (1972) Palladium-catalyzed vinylic hydrogen substitution reactions
with aryl, benzyl, and styryl halides. J Org Chem 37:2320–2322. https://doi.org/10.1021/
jo00979a024
7. Keller G (1982) Synthesis of ethylene via oxidative coupling of methane I. Determination of
active catalysts. J Catal 73:9–19. https://doi.org/10.1016/0021-9517(82)90075-6
1 Introduction
1.4 Development and Outlook
Currently, tremendous amount of excellent work is still publishing on oxidative
cross-couplings between two different nucleophiles especially those C-H nucleophiles. However, challenges still remain in this research area, such as the selective
control of the reactive site of hydrocarbons. Moreover, understandings of this concept are still superficial and incomplete, and the mechanistic study in this area is
still in its primary stage. Along with the development of transition metal-catalyzed
oxidative cross-couplings, especially of those none noble transition metal catalysis
system, radical process becomes dominating in the research area. More and more
examples will be developed in the future. And there are still many unexplored
methods and unknown insightful mechanism left. Therefore, chances and challenges are still remaining, such as finding milder reaction conditions and proper
ways to control the reactivity and chemoselectivity of radical species. Thus developing new, greener, and more efficient radical oxidative cross-couplings is still an
urgent work in the future. Furthermore, external oxidant-free oxidative cross-coupling between two C-H with the release of hydrogen gas would be a very promising
direction for oxidative cross-couplings. This area is more atomic economy and consistent with sustainable development, with no wasteful by-products or oxidation
side reactions, and the environment is sustainable. It holds significant potential for
the applications to a series of organic reactions, and scientists paid more and more
attention on this field.
References
1. Baba S, Negishi E (1976) A novel stereospecific alkenyl-alkenyl cross-coupling by a palladium- or nickel-catalyzed reaction of alkenylalanes with alkenyl halides. J Am Chem Soc
98:6729–6731. https://doi.org/10.1021/ja00437a067
2. Ghose R, Hwang HT, Varma A (2014) Oxidative coupling of methane using catalysts synthesized by solution combustion method: catalyst optimization and kinetic studies. Appl Catal A
472:39–46. https://doi.org/10.1016/j.apcata.2013.12.004
3. Glaser C (1869) Beiträge zur Kenntniss des Acetenylbenzols. Ber Dtsch Chem Ges 2:422–
424. https://doi.org/10.1002/cber.186900201183
4. Guram AS, Rennels RA, Buchwald SL (1995) A simple catalytic method for the conversion
of aryl bromides to Arylamines. Angew Chem Int Ed 34:1348–1350. https://doi.org/10.1002/
anie.199513481
5. Hatanaka Y, Hiyama T (1988) Cross-coupling of organosilanes with organic halides mediated
by a palladium catalyst and tris(diethylamino)sulfonium difluorotrimethylsilicate. J Org Chem
53:918–920. https://doi.org/10.1021/jo00239a056
6. Heck RF, Nolley JP (1972) Palladium-catalyzed vinylic hydrogen substitution reactions
with aryl, benzyl, and styryl halides. J Org Chem 37:2320–2322. https://doi.org/10.1021/
jo00979a024
7. Keller G (1982) Synthesis of ethylene via oxidative coupling of methane I. Determination of
active catalysts. J Catal 73:9–19. https://doi.org/10.1016/0021-9517(82)90075-6
1 Introduction