39579-27-6Relevant academic research and scientific papers
A Chiral Nitrogen Ligand for Enantioselective, Iridium-Catalyzed Silylation of Aromatic C?H Bonds
Su, Bo,Zhou, Tai-Gang,Li, Xian-Wei,Shao, Xiao-Ru,Xu, Pei-Lin,Wu, Wen-Lian,Hartwig, John F.,Shi, Zhang-Jie
supporting information, p. 1092 - 1096 (2017/01/18)
Iridium catalysts containing dative nitrogen ligands are highly active for the borylation and silylation of C?H bonds, but chiral analogs of these catalysts for enantioselective silylation reactions have not been developed. We report a new chiral pyridiny
Bipyridine- and phenanthroline-based metal-organic frameworks for highly efficient and tandem catalytic organic transformations via directed C-H activation
Manna, Kuntal,Zhang, Teng,Greene, Francis X.,Lin, Wenbin
supporting information, p. 2665 - 2673 (2015/03/04)
We report here the synthesis of a series of robust and porous bipyridyl- and phenanthryl-based metal-organic frameworks (MOFs) of UiO topology (BPV-MOF, mBPV-MOF, and mPT-MOF) and their postsynthetic metalation to afford highly active single-site solid catalysts. While BPV-MOF was constructed from only bipyridyl-functionalized dicarboxylate linker, both mBPV- and mPT-MOF were built with a mixture of bipyridyl- or phenanthryl-functionalized and unfunctionalized dicarboxylate linkers. The postsynthetic metalation of these MOFs with [Ir(COD)(OMe)]2 provided Ir-functionalized MOFs (BPV-MOF-Ir, mBPV-MOF-Ir, and mPT-MOF-Ir), which are highly active catalysts for tandem hydrosilylation of aryl ketones and aldehydes followed by dehydrogenative ortho-silylation of benzylicsilyl ethers as well as C-H borylation of arenes using B2pin2. Both mBPV-MOF-Ir and mPT-MOF-Ir catalysts displayed superior activities compared to BPV-MOF-Ir due to the presence of larger open channels in the mixed-linker MOFs. Impressively, mBPV-MOF-Ir exhibited high TONs of up to 17000 for C-H borylation reactions and was recycled more than 15 times. The mPT-MOF-Ir system is also active in catalyzing tandem dehydrosilylation/dehydrogenative cyclization of N-methylbenzyl amines to azasilolanes in the absence of a hydrogen acceptor. Importantly, MOF-Ir catalysts are significantly more active (up to 95 times) and stable than their homogeneous counterparts for all three reactions, strongly supporting the beneficial effects of active site isolation within MOFs. This work illustrates the ability to increase MOF open channel sizes by using the mixed linker approach and shows the enormous potential of developing highly active and robust single-site solid catalysts based on MOFs containing nitrogen-donor ligands for important organic transformations.
Rhodium-catalyzed enantioselective silylation of arene C-H bonds: Desymmetrization of diarylmethanols
Lee, Taegyo,Wilson, Tyler W.,Berg, Robert,Ryberg, Per,Hartwig, John F.
, p. 6742 - 6745 (2015/06/16)
We report a Rh-catalyzed, enantioselective silylation of arene C-H bonds directed by a (hydrido)silyl group. (Hydrido)silyl ethers that are formed in situ by hydrosilylation of benzophenone or its derivatives undergo asymmetric C-H silylation in high yiel
Iridium-catalyzed arene ortho -silylation by formal hydroxyl-directed C-H activation
Simmons, Eric M.,Hartwig, John F.
supporting information; experimental part, p. 17092 - 17095 (2011/03/01)
A strategy for the ortho-silylation of aryl ketone, benzaldehyde, and benzyl alcohol derivatives has been developed in which a hydroxyl group formally serves as the directing element for Ir-catalyzed arene C-H bond activation. One-pot generation of a (hyd
