Depending on the nature of the ligand or the counteranion to which it is coordinated, indium(I) can act as both a Lewis add and a Lewis base because It has both vacant p orbitals and a lone pair of electrons. This potential ambiphilicity may offer unique reactivity and unusual selectivity Vorinostat HDAC1 in synthesis Inhibitors,Modulators,Libraries and may have significant implications for catalysis, particularly for dual catalytic processes. We envisioned that indium(I) could be employed as a metallic Lewis base catalyst to activate Lewis acidic boron-based pronucleophiles for selective bond formation with suitable electrophiles. Alternatively, indium(I) could serve as an ambiphilic catalyst that activates both reagents at a single center.

In this Account, we describe the development of low-oxidation state indium catalysts for carbon-carbon bond formation between boron-based pronucleophiles Inhibitors,Modulators,Libraries and various electrophiles.

We discovered that indium(I) iodide was an excellent Inhibitors,Modulators,Libraries catalyst for alpha-selective allylations of C(sp(2)) electrophiles such as ketones and hydrazones. Using a combination of this low-oxidation state indium compound and a chiral semicorrin ligand, we developed catalytic highly Inhibitors,Modulators,Libraries enantioselective allylation, crotylation, and alpha-chloroallylation reactions of hydrazones. These transformations proceeded with rare constitutional selectivities and remarkable diastereoselectivities. Furthermore, indium(I) triflate served as the most effective catalyst for allylations and propargylations of C(sp(3)) electrophiles such as O,O-acetals, N,O-aminals, and ethers, and we applied this methodology to carbohydrate chemistry.

In addition, a catalyst system composed of indium(I) chloride and a chiral silver BINOL-phosphate facilitated the highly enantioselective allylation and allenylation of N,O-aminals. Overall, these discoveries demonstrate the versatility, efficiency, and sensitivity of low-oxidation state indium catalysts in organic synthesis.”
“Chiral diamines AV-951 are important building blocks for constructing stereoselective catalysts, including transition metal based catalysts and organocatalysts that facilitate oxidation, reduction, hydrolysis, and C-C bond forming reactions. These molecules are also critical components in the synthesis of drugs, including antiviral agents such as Tamiflu and Relenza and anticancer agents such as oxaliplatin and nutlin-3.

The diaza-Cope rearrangement reaction provides one of the most versatile methods for rapidly generating a wide variety of chiral diamines stereospecifically and under mild conditions. Weak forces Perifosine KRX-0401 such as hydrogen bonding, electronic, steric, oxyanionic, and conjugation effects can drive this equilibrium process to completion.

In this Account, we examine the effect of these individual weak forces on the value of the equilibrium constant for the diaza-Cope rearrangement reaction using both computational and experimental methods.