Solvolysis in dipolar aprotic media. II. Initial rates of bromide ion production from tertiary alkyl bromides in dimethylformamide, measured in situ. Proposal of a solvolysis scheme for 2-bromo-2-methylpentane

1975 ◽  
Vol 40 (3) ◽  
pp. 312-318 ◽  
Author(s):  
Hendrik L. Peeters ◽  
Marc Anteunis
Keyword(s):  
Alkyl Bromides ◽  
Ion Production ◽  
Bromide Ion ◽  
Tertiary Alkyl

Zn- and Cu-Catalyzed Coupling of Tertiary Alkyl Bromides and Oxalates to Forge Challenging C–O, C–S, and C–N Bonds

2021 ◽  
Vol 23 (3) ◽  
pp. 1005-1010
Author(s):  
Yuxin Gong ◽  
Zhaodong Zhu ◽  
Qun Qian ◽  
Weiqi Tong ◽  
Hegui Gong
Keyword(s):  
Alkyl Bromides ◽  
Tertiary Alkyl

ChemInform Abstract: Silver-Catalyzed Benzylation and Allylation of Tertiary Alkyl Bromides with Organozinc Reagents.

ChemInform ◽  
2010 ◽  
Vol 41 (42) ◽  
Author(s):  
Yukihiro Mitamura ◽  
Yoshihiro Asada ◽  
Kei Murakami ◽  
Hidenori Someya ◽  
Hideki Yorimitsu ◽  
...  
Keyword(s):  
Alkyl Bromides ◽  
Organozinc Reagents ◽  
Tertiary Alkyl

scholarly journals Copper-catalyzed direct alkylation of heteroarenes

2017 ◽  
Vol 8 (5) ◽  
pp. 3465-3470 ◽  
Author(s):  
Cédric Theunissen ◽  
Jianjun Wang ◽  
Gwilherm Evano
Keyword(s):  
Alkyl Radicals ◽  
Alkyl Bromides ◽  
Tertiary Alkyl

An efficient and broadly applicable process is reported for the direct alkylation of heteroarene C–H bonds, based on the copper-catalyzed addition of alkyl radicals generated from activated secondary and tertiary alkyl bromides to a range of arenes, and their benzo-fused derivatives.

Retaining Alkyl Nucleophile Regiofidelity in Transition-Metal-Mediated Cross-Couplings to Aryl Electrophiles

Synthesis ◽  
2018 ◽  
Vol 50 (20) ◽  
pp. 3974-3996 ◽  
Author(s):  
Josep Cornella ◽  
Matthew O’Neill
Keyword(s):  
Transition Metal ◽  
Functional Group ◽  
Chemical Space ◽  
Cross Coupling ◽  
Transition Metal Catalysis ◽  
Metal Catalysis ◽  
Substantial Progress ◽  
Tertiary Alkyl ◽  
Metal Ligand

While the advent of transition-metal catalysis has undoubtedly transformed synthetic chemistry, problems persist with the introduction of secondary and tertiary alkyl nucleophiles into C(sp2) aryl electrophiles. Complications arise from the delicate organometallic intermediates typically invoked by such processes, from which competition between the desired reductive elimination event and the deleterious β-H elimination pathways can lead to undesired isomerization of the incoming nucleophile. Several methods have integrated distinct combinations of metal, ligand, nucleophile, and electrophile to provide solutions to this problem. Despite substantial progress, refinements to current protocols will facilitate the realization of complement reactivity and improved functional group tolerance. These issues have become more pronounced in the context of green chemistry and sustainable catalysis, as well as by the current necessity to develop robust, reliable cross-couplings beyond less explored C(sp2)–C(sp2) constructs. Indeed, the methods discussed herein and the elaborations thereof enable an ‘unlocking’ of accessible topologically enriched chemical space, which is envisioned to influence various domains of application.1 Introduction2 Mechanistic Considerations3 Magnesium Nucleophiles4 Zinc Nucleophiles5 Boron Nucleophiles6 Other Nucleophiles7 Tertiary Nucleophiles8 Reductive Cross-Coupling with in situ Organometallic Formation9 Conclusion

A Direct Functionalization of Tertiary Alkyl Bromides with O-, N-, and C-Nucleophiles.

ChemInform ◽  
2007 ◽  
Vol 38 (46) ◽  
Author(s):  
Petr Vachal ◽  
Joan M. Fletcher ◽  
William K. Hagmann
Keyword(s):  
Alkyl Bromides ◽  
Direct Functionalization ◽  
Tertiary Alkyl

scholarly journals One-Step Synthesis of Acylboron Compounds via Cu-Catalyzed Carbonylative Borylation of Alkyl Halides

2020 ◽  
Author(s):  
Cheng Li-Jie ◽  
Zhao Siling ◽  
Neal Mankad
Keyword(s):  
Alkyl Halides ◽  
Efficient Synthesis ◽  
Mechanistic Studies ◽  
Acyl Halide ◽  
Reaction Conditions ◽  
One Pot ◽  
One Step ◽  
High Yields ◽  
Tertiary Alkyl

A Cu-catalyzed carbonylative borylation of unactivated alkyl halides has been developed, enabling efficient synthesis of aliphatic potassium acyltrifluoroborates (KATs) in high yields by treating the in-situ formed tetracoordinated acylboron intermediates with aqueous KHF2. A variety of functional groups are tolerated under the mild reaction conditions, and primary, secondary and tertiary alkyl halides are all applicable. In addition, this method also provides facile access to N-methyliminodiacetyl (MIDA) acylboronates as well as α-methylated potassium acyltrifluoroborates in a one-pot manner. Mechanistic studies indicate a radical atom transfer carbonylation (ATC) mechanism to form acyl halide intermediates that are subsequently borylated by (NHC)CuBpin.<br>

Irradiation-Induced Palladium-Catalyzed Direct C–H Alkylation of Heteroarenes with Tertiary and Secondary Alkyl Bromides

Synthesis ◽  
2018 ◽  
Vol 50 (15) ◽  
pp. 2908-2914 ◽  
Author(s):  
Rui Shang ◽  
Yao Fu ◽  
Guang-Zu Wang
Keyword(s):  
Blue Light ◽  
Palladium Catalyst ◽  
Light Emitting Diodes ◽  
Oxidative Addition ◽  
Phosphine Ligands ◽  
Light Emitting ◽  
Alkyl Radicals ◽  
Alkyl Bromides ◽  
Palladium Catalyzed ◽  
Tertiary Alkyl

A palladium catalyst in combination with two types of phosphine ligands efficiently catalyzes direct C–H alkylation of heteroarenes with secondary and tertiary alkyl bromides under irradiation conditions. Irradiation of blue light-emitting diodes (blue LEDs) effectively excites phosphine-ligated palladium catalyst to facilitate oxidative addition with alkyl bromides, and also excites the alkylpalladium species to enable the generation of alkyl radicals to react with heteroarenes.

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