No abstract

No abstract

For catalytic asymmetric hydroformylation (AHF) of alkenes to chiral aldehydes, though a topic of high interest, the contemporary developments remain largely empirical owing to rather limited molecular insights on the origin of enantioselectivity. Given this gap, herein, we present the mechanistic details of Rh-(S,S)-YanPhoscatalyzed AHF of α-methylstyrene, as obtained through a comprehensive DFT (ω-B97XD and M06) study. The challenges with the double axially chiral YanPhos, bearing an N-benzyl BINOL-phosphoramidite and a BINAP-bis(3,5-t-Bu-aryl)phosphine, are addressed through exhaustive conformational sampling. The C−H•••π, π•••π, and lone pair•••π noncovalent interactions (NCIs) between the N-benzyl and the rest of the chiral ligand limit the N-benzyl conformers. Similarly, the C−H•••π and π•••π NCIs between the chiral catalyst and α-methylstyrene render the siface binding to the Rh-center more preferred over the re-face. The transition state (TS) for the regiocontrolling migratory insertion, triggered by the Rh-hydride addition to the alkene, to the more substituted α-carbon is 3.6 kcal/mol lower than that to the β-carbon, thus favoring the linear chiral aldehyde over the achiral branched alternative. In the linear pathway, the TS for the hydride addition to the si-face is 1.5 kcal/mol lower than that to the re-face, with a predicted ee of 85% for the S aldehyde (expt. 87%). The energetic span analysis reveals the reductive elimination as the turnover determining step for the preferred S linear aldehyde. These molecular insights could become valuable for exploiting AHF reactions for substituted alkenes and for eventual industrial implementation.

No abstract

SUMMARY Most natural gas (NG) producers in the Persian Gulf face increasing challenges in meeting their domestic gas demands and therefore seek to reduce their NG consumption. Concurrently, the on‐site power generation and cooling capacities of local NG processing facilities are constrained by extreme climatic conditions. A combined cooling and power scheme based on gas turbine (GT) waste heat‐powered absorption refrigeration is techno‐economically assessed to reduce the NG consumption of a major gas processing plant in the Persian Gulf. The scheme utilizes double‐effect water‐lithium bromide absorption refrigeration activated by steam generated from GT exhaust gas waste heat to provide both GT compressor inlet air and process gas cooling. Based on a thermodynamic analysis, recovery of 150 MW of GT waste heat is found to enhance the plant cooling capacity by 195 MW, thereby permitting elimination of a 32.6 MW GT and existing cooling equipment. On‐site power generation is enhanced by 196 GWh annually through GT compressor inlet air cooling, with energy efficiency (i.e., 64%) improved by 35% using cogeneration relative to the existing power generation plant. The overall net annual operating expenditure savings contributed by the combined cooling and power system are of $US13 million to 34 million based on present and projected local utility prices, with an economic payback period estimated at 2 to 5 years. These savings translate to approximately 94 to 241 MMSCM of NG per year, highlighting the potential of absorption refrigeration to both enhance the power generation and cooling capacity of hydrocarbon processing plants exposed to harsh environmental conditions and to realize substantial primary energy savings. Copyright © 2014 John Wiley & Sons, Ltd.