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Palladium-Catalyzed Reductive Cross- Coupling Reactions and The

Analysis of
Site-Selectivity in Rhodium-Catalyzed C-H Amination Reactions
By Dr. Ryan DeLuca
Sigman Group U of U
By Danielle Deluca-Loumis
The research paper gives a detailed account of reductive cross-coupling methods. These
types of transition metal-catalyzed cross-coupling strategies have been widely used in the
chemical community for the formation of carbon-carbon bonds. The extension of Pdcatalyzed cross-coupling technology that includes sp3-sp3 Cross-Coupling has been slow
to be realized due to facile -hydride elimination of kinetically unstable Pd-alkyl
intermediates.

This research paper examines pioneering studies of cross-coupling

reactions. Alternative methods are cited, but the focus of this thesis is new substratecontrolled alkene hydrofunctionalization reactions by the Sigman laboratory at the
University of Utah. This research ultimately led to a selective Pd-catalyzed antiMarkovnikov hydroalkylation reaction using terminal allyic-substituted alkenes and
alkylzinc reagents.

Dr. DeLuca explored the tendency of Pd-alkyll intermediates to undergo facile -hydride
elimination as a way to furnish Pd-hydrides for further reaction. The Sigman group
decided to intercept the Pd-hydrides with alkenyl substrates. The results of this study
concluded that a multitude of unreactive reaction sites could now be assessed.

The group decided they wanted to investigate the factors controlling the site-selectivity
of Rh-catalyzed intermolecular C-H sulfamintation reactions be of aliphatic substrates

containing both benzilic and tertiary C-H bonds. The selective catalytic functionalization
of C-H bonds is one of the biggest challenges in organic chemistry. This type of bong
however, has potential to fundamentally streamline retrosynthetic approaches in modern
organic strategies.

Selective functionalization of C-H bonds has the potential to

revolutionize organic synthesis. The C-N bond using selective C-H functionalization is
attractive due to the prevalence of nitrogen groups in many drugs and natural products.
Through the years many advances have been realized in the field of rhodium-catalyzed
aliphatic C-H amination. The research goes on to site several previous studies and what
each was used from each study to help with Dr. DeLucas new thesis. One such study
intrigued Dr. Delucas group.

They used preliminary site-selectivity data from Dr.

Duboiss group. DeLucas group started investigating the role of the steric and electronic
nature of the sulfimate ester reagent. They collected a set of data of B:T ratios using
isoamylbenzeneas as a substrate.
A diverse sulfimate esters were designed they concluded it was important to seek
maximal variations of the R-groups on the sulfimate in order to fully evaluate what
characteristics intimately influence product selectivity.

They also explored chlorine

substitutes systematically. They introduced monochloromethyl 1 groups at the terminal


end of the alkyl chain. This produces similar ratios to the B:T ratios.
The research and data in DeLucas published thesis gives Organic Chemists great odds on
Rh-catalyzed transformation. Also I should note One of the other groups discovered an
interesting reaction they observed with optimized conditions of H 202 complete substrate
consumption is diarylmethine motif a compound that exhibits antiproliferative activity

against certain breast cancer cells. They have come very far in their recent discoveries,
but they still have a lot to learn from their data.