Ni-Catalyzed Regioselective 1,2-Dialkylation of Alkenes Enabled by the Formation of Two C(sp3)-C(sp3) Bonds.

@article{Dhungana2020NiCatalyzedR1,
  title={Ni-Catalyzed Regioselective 1,2-Dialkylation of Alkenes Enabled by the Formation of Two C(sp3)-C(sp3) Bonds.},
  author={Roshan K. Dhungana and Rishi R Sapkota and Laura M. Wickham and Doleshwar Niroula and Ramesh Giri},
  journal={Journal of the American Chemical Society},
  year={2020}
}
We disclose a Ni-catalyzed vicinal difunctionalization of alkenes with benzyl halides and alkylzinc reagents, which produces products with two new alkyl-alkyl bonds. This alkene dialkylation is effective in combining secondary benzyl halides and secondary alkylzinc reagents with internal alkenes, which furnishes products with three contiguous all-carbon secondary stereocenters. The products can be readily elaborated to access complex tetralene, benzosuberene, and bicyclodecene cores. The… 
12 Citations
Directed Nickel-Catalyzed Diastereoselective Reductive Difunctionalization of Alkenyl Amines.
TLDR
This general and practical protocol is compatible with α- or β-substituted terminal alkenes and internalAlkenes, providing rapid access to branched aliphatic amines bearing two skipped and vicinal stereocenters with high diastereoselectivities that would otherwise be difficult to synthesize.
Nickel-Catalyzed Chemo- and Regioselective Benzylarylation of Unactivated Alkenes with o-Bromobenzyl Chlorides.
Chemo- and regioselectively nickel-catalyzed reductive benzylarylation of unactivated alkenes with o-bromobenzyl chlorides is disclosed herein, in which electrophiles participate through a
Lewis Acid-Catalyzed Halonium Generation for Morpholine Synthesis and Claisen Rearrangement.
We disclose here practical strategies toward the synthesis of morpholines and Claisen rearrangement products based on the divergent reactivity of a common halonium intermediate. These reactions
Radical-mediated alkoxypolyhaloalkylation of styrenes with polyhaloalkanes and alcohols via C(sp3)-H bond cleavage.
TLDR
A new radical-mediated alkoxypolyhaloalkylation of styrenes with polychloroalkanes and alcohols for the facile synthesis of complex polyhaloalcohols and cholesterol derivatives is developed.
Photoinduced 1,2-dicarbofunctionalization of alkenes with organotrifluoroborate nucleophiles via radical/polar crossover†
TLDR
An intermolecular 1,2-dicarbofunctionalization using alkyl N-(acyloxy)phthalimide redox-active esters as radical progenitors and organotrifluoroborates as carbon-centered nucleophiles is reported, postulated to proceed through photochemical radical/polar crossover to afford a key carbocation species.
Transition Metal (Ni, Cu, Pd)-Catalyzed Alkene Dicarbofunctionalization Reactions.
TLDR
Examples of alkene dicarbofunctionalization reactions demonstrate that Cu and Ni catalysts could enable cyclization/coupling of alkenylzinc reagents, alkyl halide, and aryl halides to afford complex carbo- and heterocycles.
Chiral Hypervalent Iodine Catalysis Enables an Unusual Regiodivergent Intermolecular Olefin Aminooxygenation
TLDR
A novel iodide-catalyzed intermolecular aminooxygenation strategy based on nucleophile can also be applied in asymmetric processes using chiral hypervalent iodine catalysis.
Access to the C2 C–H olefination, alkylation and deuteration of indoles by rhodium(iii) catalysis: an opportunity for diverse syntheses
A concise approach for a diversity-oriented synthesis via regioselective C2 C–H olefination, alkylation, and deuteration of indoles by Rh(iii) catalysis is described.
Catalytic three-component dicarbofunctionalization reactions involving radical capture by nickel.
TLDR
Recent advances in catalytic dicarbofunctionalization of unsaturated π bonds are summarized by underpinning the catalytic domino transformations involving radical capture by nickel to provide a clear overview of reaction designs and mechanistic scenarios.
...
1
2
...

References

SHOWING 1-10 OF 60 REFERENCES
Ni-Catalyzed Regioselective Alkylarylation of Vinylarenes via C(sp3)-C(sp3)/C(sp3)-C(sp2) Bond Formation and Mechanistic Studies.
TLDR
A Ni-catalyzed regioselectiveAlkylarylation of vinylarenes with alkyl halides and arylzinc reagents to generate 1,1-diarylalkanes is reported, revealing that the current reaction proceeds via a Ni(0)/Ni(I)/ Ni(II) catalytic cycle.
Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles.
TLDR
This approach utilizes a readily removable imine as a coordinating group that plays a dual role of intercepting oxidative addition species derived from aryl halides and triflates to promote Heck carbometalation and stabilizing the Heck C(sp3)-NiX intermediates as transient metallacycles to suppress β-hydride elimination and facilitate transmetalation/reductive elimination steps.
Nickel-Catalyzed 1,2-Diarylation of Alkenyl Carboxylates: A Gateway to 1,2,3-Trifunctionalized Building Blocks.
TLDR
This method represents the first example of catalytic 1,2-diarylation of an alkene directed by a native carboxylate group and improves three routes toward bioactive molecules in terms of yield and/or step count.
Nickel-Catalyzed Dicarbofunctionalization of Alkenes.
TLDR
Great opportunities exist for the development of three-component difunctionalization reactions with broad substrate scopes and tunable chemo-, regio-, and stereoselectivities.
Nickel-Catalyzed β,γ-Dicarbofunctionalization of Alkenyl Carbonyl Compounds via Conjunctive Cross-Coupling.
TLDR
The methodology developed herein represents the first three-component 1,2-dicarbofunctionalization of non-conjugated alkenes involving a C(sp3)-C( sp3) reductive elimination step.
Three-Component Ruthenium-Catalyzed Direct meta-Selective C-H Activation of Arenes: A New Approach to The Alkylarylation of Alkenes.
TLDR
An unprecedented three-component direct C-H addition was achieved in the challenging meta-selective fashion and provided access to various fluoride-containing bioactive 1,1-diarylalkanes and other challenging synthetically potential products.
Nickel-Catalyzed 1,2-Diarylation of Simple Alkenyl Amides.
TLDR
This method represents the first example of regiocontrolled 1,2-diarylation directed by a native amide functional group and sheds light on the potential substrate binding mode and the role of the EDO ligand in the reductive elimination step.
Nickel-Catalyzed Reductive 1,2-Dialkynylation of Alkenes Bearing an 8-Aminoquinoline Directing Group.
TLDR
An unprecedented nickel-catalyzed reductive 1,2-dialkynylation of alkenes bearing an 8-aminoquinoline directing group has been developed, providing direct access to the synthetically flexible 1,5-diynes.
Palladium-catalyzed oxidative intermolecular difunctionalization of terminal alkenes with organostannanes and molecular oxygen.
TLDR
A cationic palladium complex catalyzes the title transformations, which are thought to proceed via a pi-allyl or pi-benzyl intermediate and appears to be controlled by the relative rates of beta-hydride elimination and transmetalation.
Pd-Catalyzed Regioselective 1,2-Difunctionalization of Vinylarenes with Alkenyl Triflates and Aryl Boronic Acids at Ambient Temperature.
A Pd-catalyzed highly regioselective 1,2-difunctionalization of vinylarenes is disclosed in which multisubstituted olefins are efficiently and conveniently constructed under ambient temperature with
...
1
2
3
4
5
...