Double Hydroelementation of N-Heteroarenes
Sehoon Park

Departement of Chemistry, Guangdong-Technion Israel Institute of Techniology, China
sehoon.park@gtiit.edu.cn, https://sites.gtiit.edu.cn/parkgroup
Catalytic dearomative reduction of N-heteroarenes is of important transformations in organic synthesis
as well as medicinal chemistry. A number of organo(metallic) catalysts have been documented for selectivehydrosilylation and hydroboration of pyridines to provide a broad range of dihydro-products.1 However, doublehydroelementation of pyridines possibly leading to a new family of tetrahydro-products bearing a sp3 C−E bond
(E = Si, B-based moieties), had been unknown until we disclosed.
In this talk, we will describe the full aspects of the first double hydrosilylation and hydroboration ofquinolines and pyridines catalyzed by B(C6F5)3 (Figure a).2 Next, we will show the Rh-catalyzed regio- andenantioselective double hydroboration of quinolines and pyridine,3-4 where a combination of mechanistic
experiments and DFT calculations reveal the origin of the chemo- and regioselectivities. Furthermore, we will
present preliminary results on the first-row metal-catalyzed double hydroboration of quinolines and pyridines.5
These catalytic systems represent the first example of a metal-catalyzed double hydroboration of N-heteroarenes(Figure b).

(a)
[E]

Ar
N
[E]

cat. B(C6F5)3+ H[E](E = SiEt2H, Bcat)(b)cat. [M](chiral) P ligand

Ar
N+ HBpin

[B]

N

N

[B]

[B]

*
P + PRh

ArN
B(C6F5)3

Ar

[B]
*Ar

NNCl
H
Ar

sole resting species
dominant resting species[B]orN
[B]

Rh
N

PBpin
calculatedη4-complex
for cascading hydroboraionReferences
1. (a) S. Park, S. Chang, Angew. Chem. Int. Ed. 2017, 56, 7720. (b) S. Park, Chin. J. Chem. 2019, 37, 1057. (c) S.
Park, ChemCatChem 2020, 12, 3170.
2. (a) N. Gandhamsetty, S. Joung, S.-W. Park, S. Park, S. Chang, J. Am. Chem. Soc. 2014, 136, 16780. (b) N.
Gandhamsetty, S. Park, S. Chang, J. Am. Chem. Soc. 2015, 137, 15176. (c) E. Kim, S. Park, S. Chang, Adv. Synth.
Catal. 2020, 362, 308.
3. R. Wang, S. Park, ACS Catal. 2023, 13, 7067-7078.
4. H. Choi, R. Wang, S. Kim, D. Kim, M.-H. Baik, S. Park, Catal. Sci. Technol. 2023, 13, 2735-2747.
5. Manuscript in preparation.
Sehoon Park was born in Seoul (Korea) in 1977. He received his PhD degree (2008)
in chemistry from Tokyo Institute of Technology under the supervision of Professor
Kohtaro Osakada and Professor Daisuke Takeuchi. He then moved to theUniversity of North Carolina at Chapel Hill to work as a postdoctoral fellow withProfessor Maurice Brookhart (2009–2012). From April 2013 to February 2019, heworked at Institute for Basic Science (Korea) as a senior research fellow with Prof.
Sukbok Chang as a mentor. In early 2019, he started his independent research as
an assistant professor at Guangdong-Technion Israel Institute of Technology(GTIIT), where he is currently an associate professor at the Department ofChemistry. He is an associate editor for the section of Organometallic Chemistry
in Frontiers in Chemistry (IF 5.545). He has published 45 peer-reviewed papers andover 5 US patents in the area of synthetic organic chemistry. His interests are thesynthetic and mechanistic organo(metallic) catalysis.