0000000000285953
AUTHOR
Gokarneswar Sahoo
ChemInform Abstract: A Catalyst Designed for the Enantioselective Construction of Methyl- and Alkyl-Substituted Tertiary Stereocenters.
Tertiary methyl-substituted stereocenters are present in numerous biologically active natural products. Reported herein is a catalytic enantioselective method for accessing these chiral building blocks using the Mukaiyama-Michael reaction between silyl ketene thioacetals and acrolein. To enable remote enantioface control on the nucleophile, a new iminium catalyst, optimized by three-parameter tuning and by identifying substituent effects on enantioselectivity, was designed. The catalytic process allows rapid access to chiral thioesters, amides, aldehydes, and ketones bearing an α-methyl stereocenter with excellent enantioselectivities, and allowed rapid access to the C4-C13 segment of (-)-b…
Mukaiyama–Michael Reactions with trans-2,5-Diarylpyrrolidine Catalysts: Enantioselectivity Arises from Attractive Noncovalent Interactions, Not from Steric Hindrance
The scope of the enantioselective Mukaiyama-Michael reactions catalyzed by trans-2,5-diphenylpyrrolidine has been expanded to include both α- and β-substituted enals. However, the rationalization of the observed enantioselectivity is far from obvious since the catalyst is not very sterically hindered. DFT calculations were carried out to rationalize the observed stereoselectivities. Transition states of the C-C bond formation between iminium intermediates and silyloxyfurans were located and their relative energies were used to estimate the stereoselectivity data. We find excellent agreement between the predicted and observed stereoselectivities. The analysis of intermolecular forces reveals…
ChemInform Abstract: Mukaiyama-Michael Reactions with trans-2,5-Diarylpyrrolidine Catalysts: Enantioselectivity Arises from Attractive Noncovalent Interactions, Not from Steric Hindrance.
The 2,5-diphenylpyrrolidine-catalyzed enantioselective Mukaiyama—Michael reaction between substituted furans and enals is studied.
Dihydrooxazine Oxides as Key Intermediates in Organocatalytic Michael Additions of Aldehydes to Nitroalkenes
Pause and play: dihydrooxazine oxides are stable intermediates that are protonated directly, without the intermediacy of the zwitterions, in organocatalytic Michael additions of aldehydes and nitroalkenes (see scheme, R=alkyl). Protonation of these species explains both the role of the acid co-catalyst in these reactions, and the observed stereochemistry when the reaction is conducted with α-alkylnitroalkenes.
A Catalyst Designed for the Enantioselective Construction of Methyl- and Alkyl-Substituted Tertiary Stereocenters
Tertiary methyl-substituted stereocenters are present in numerous biologically active natural products. Reported herein is a catalytic enantioselective method for accessing these chiral building blocks using the Mukaiyama-Michael reaction between silyl ketene thioacetals and acrolein. To enable remote enantioface control on the nucleophile, a new iminium catalyst, optimized by three-parameter tuning and by identifying substituent effects on enantioselectivity, was designed. The catalytic process allows rapid access to chiral thioesters, amides, aldehydes, and ketones bearing an α-methyl stereocenter with excellent enantioselectivities, and allowed rapid access to the C4-C13 segment of (-)-b…
ChemInform Abstract: Dihydrooxazine Oxides as Key Intermediates in Organocatalytic Michael Additions of Aldehydes to Nitroalkenes.
Pause and play: dihydrooxazine oxides are stable intermediates that are protonated directly, without the intermediacy of the zwitterions, in organocatalytic Michael additions of aldehydes and nitroalkenes (see scheme, R=alkyl). Protonation of these species explains both the role of the acid co-catalyst in these reactions, and the observed stereochemistry when the reaction is conducted with α-alkylnitroalkenes.
Characterization of Hardwood Soda-AQ Lignins Precipitated from Black Liquor through Selective Acidification
In the development of integrated biorefinery process alternatives to produce value-added by-products, various black liquors from sulfur-free pulping processes offer potential feedstocks for recovering their main chemical constituents, lignin and aliphatic carboxylic acids. In this study, lignin fractions were obtained from silver birch (Betula pendula) soda-anthraquinone black liquor by carbonation (pH to about 8.5) or by acidification (pH to about 2) with H2SO4 after carbonation or directly. These fractions were characterized by Fourier transform infrared (FTIR), ultraviolet (UV), energy dispersive X-ray fluorescence (ED XRF), and 13C nuclear magnetic resonance (13C NMR) spectroscopy. In a…
ReO as a Brønsted acidic modifier in glycerol hydrodeoxygenation : Computational insight into the balance between acid and metal catalysis
A computational study for the competitive conversion of glycerol to 1,2-propanediol and 1,3-propanediol is presented, considering a two-step sequence of dehydration followed by hydrogenation. The elementary steps for dehydration, i.e., breaking of C–H followed by C–OH or vice versa, were studied computationally both on the Rh metal surface and the acid-modified ReOH–Rh surface in order to understand the role of the acid promoter. While the acid modifier can catalyze the C–OH cleavage, the activation energy for the C–H cleavage was found to be considerably smaller on both pure and acid-doped Rh(111) surfaces, and breaking the secondary C–H bond is kinetically favored over breaking the termin…
Mukaiyama–Michael Reactions with Acrolein and Methacrolein: A Catalytic Enantioselective Synthesis of the C17–C28 Fragment of Pectenotoxins
Enantioselective iminium-catalyzed reactions with acrolein and methacrolein are rare. A catalytic enantioselective Mukaiyama-Michael reaction that readily accepts acrolein or methacrolein as substrates, affording the products in good yields and 91-97% ee, is presented. As an application of the methodology, an enantioselective route to the key C17-C28 segment of the pectenotoxin using the Mukaiyama-Michael reaction as the key step is described.