Temperature-Controlled Bidirectional Enantioselectivity in Asymmetric Hydrogenation Reactions Utilizing Stereodynamic Iridium Complexes

Synthesis ◽  
2017 ◽  
Vol 49 (15) ◽  
pp. 3485-3494 ◽  
Author(s):  
Max Siebert ◽  
Golo Storch ◽  
Frank Rominger ◽  
Oliver Trapp
Keyword(s):  
Elevated Temperatures ◽  
Asymmetric Hydrogenation ◽  
Iridium Complexes ◽  
Chirality Transfer ◽  
Iridium Catalysts ◽  
Thermal Equilibration ◽  
Hydrogenation Reactions ◽  
Temperature Controlled ◽  
First Time ◽  
Solid State Structures

Stereochemically flexible 2,2(-bis(diphenylphosphino)biphenyl (BIPHEP) ligands were modified with chiral α-substituted carboxylic acid auxiliaries in the 3- and 3′-position. The resulting central-to-axial chirality transfer to the stereochemically flexible chiral axis of the BIPHEP­ core was investigated as well as complexation of these diastereomeric ligands to iridium(I). Solid-state structures of both ligand diastereomers and a diastereomerically pure iridium(I) BIPHEP complex were obtained. Thermal equilibration of the resulting iridium(I) complexes was studied to investigate the stereodynamic properties of the BIPHEP ligands. The iridium(I) complexes without and after pre-catalysis warming in solution — which induces a shift of the diastereomeric ratio — were applied for asymmetric hydrogenation of a prochiral α-substituted acrylic acid, resulting in temperature-controlled bidirectional enantioselectivity of iridium catalysts for the first time. In both cases, enantioenriched (R)-naproxen as well as (S)-naproxen — after re-equilibration of the catalyst at elevated temperatures — was obtained by using the same catalyst.

Mesoporous silica-supported iridium catalysts for asymmetric hydrogenation reactions

2010 ◽  
Vol 20 (10) ◽  
pp. 1970 ◽  
Author(s):  
Guohua Liu ◽  
Jianyao Wang ◽  
Tianzeng Huang ◽  
Xiaohui Liang ◽  
Yuli Zhang ◽  
...  
Keyword(s):  
Mesoporous Silica ◽  
Asymmetric Hydrogenation ◽  
Iridium Catalysts ◽  
Hydrogenation Reactions

scholarly journals Asymmetric Hydrogenation of 1-aryl substituted-3,4-Dihydroisoquinolines with Iridium Catalysts Bearing Different Phosphorus-Based Ligands

Catalysts ◽  
2020 ◽  
Vol 10 (8) ◽  
pp. 914
Author(s):  
Giorgio Facchetti ◽  
Michael S. Christodoulou ◽  
Eleonora Binda ◽  
Marco Fusè ◽  
Isabella Rimoldi
Keyword(s):  
Asymmetric Hydrogenation ◽  
Catalytic Performance ◽  
Phosphine Ligand ◽  
Iridium Complexes ◽  
Complete Conversion ◽  
Catalytic Systems ◽  
Iridium Catalysts ◽  
Substituted 1

Starting from the chiral 5,6,7,8-tetrahydroquinolin-8-ol core, a series of amino-phosphorus-based ligands was realized. The so-obtained amino-phosphine ligand (L1), amino-phosphinite (L2) and amino-phosphite (L3) were evaluated in iridium complexes together with the heterobiaryl diphosphines tetraMe-BITIOP (L4), Diophep (L5) and L6 and L7 ligands, characterized by mixed chirality. Their catalytic performance in the asymmetric hydrogenation (AH) of the model substrate 6,7-dimethoxy-1-phenyl-3,4-dihydroisoquinoline 1a led us to identify Ir-L4 and Ir-L5 catalysts as the most effective. The application of these catalytic systems to a library of differently substituted 1-aryl-3,4-dihydroisoquinolines afforded the corresponding products with variable enantioselective levels. The 4-nitrophenyl derivative 3b was obtained in a complete conversion and with an excellent 94% e.e. using Ir-L4, and a good 76% e.e. was achieved in the reduction of 2-nitrophenyl derivative 6a using Ir-L5.

Diphosphinoazine Rhodium(I) and Iridium(I) Complexes

2006 ◽  
Vol 71 (2) ◽  
pp. 197-206 ◽  
Author(s):  
Martin Pošta ◽  
Jan Čermák ◽  
Pavel Vojtíšek ◽  
Ivana Císařová
Keyword(s):  
Rhodium Complexes ◽  
Iridium Complexes ◽  
X Ray ◽  
First Time

The first rhodium complexes of diphosphinoazines [{RhCl(1,2-η:5,6-η-CH=CHCH2CH2CH=CHCH2CH2)}2 {μ-R2PCH2C(But)=NN=C(But)CH2PR2] (R = Ph, Cy, Pri) were prepared by cleavage of the bridge in chloro(cycloocta-1,5-diene)rhodium(I) dimer, the analogous iridium(I) complexes were also prepared for the first time. The X-ray structures of isostructural rhodium and iridium complexes with bis(dicyclohexylphosphino)pinacoloneazine were determined. Diphosphinoazine ligands in the complexes remained in (Z,Z) configuration bridging two RhCl(C8H12) units.

Catalytic asymmetric hydrogenation reaction by in situ formed ultra-fine metal nanoparticles in live thermophilic hydrogen-producing bacteria

Nanoscale ◽  
2021 ◽  
Author(s):  
Wei Bing ◽  
Faming Wang ◽  
Yuhuan Sun ◽  
Jinsong Ren ◽  
Xiaogang Qu
Keyword(s):  
Metal Nanoparticles ◽  
Catalytic Hydrogenation ◽  
Asymmetric Hydrogenation ◽  
Environmentally Friendly ◽  
Hydrogenation Reaction ◽  
Highly Efficient ◽  
Hydrogenation Reactions ◽  
Live Bacteria ◽  
Catalytic Asymmetric Hydrogenation

An environmentally friendly biomimetic strategy has been presented and validated for the catalytic hydrogenation reaction in live bacteria. In situ formed ultra-fine metal nanoparticles can realize highly efficient asymmetric hydrogenation reactions.

Gold(I) Complexes Bearing P∩N-Ligands: An Unprecedented Twelve-membered Ring Structure Stabilized by Aurophilic Interactions

2009 ◽  
Vol 64 (11-12) ◽  
pp. 1513-1524 ◽  
Author(s):  
Uwe Monkowius ◽  
Manfred Zabel ◽  
Michel Fleck ◽  
Hartmut Yersin
Keyword(s):  
Solid State ◽  
Ring Structure ◽  
Phosphine Ligands ◽  
X Ray Crystallography ◽  
Aggregation Pattern ◽  
Elemental Analyses ◽  
High Yields ◽  
First Time ◽  
Solid State Structures ◽  
Aurophilic Interactions

The P∩N-ligands Ph2Pqn, 1, Ph2 Piqn, 2, Ph2 Ppym, 3, and the As∩N-ligands Ph2Asqn, 4, Ph2Asiqn, 5, (Ph = phenyl, qn = 8-quinoline, iqn = 1-isoquinoline, pym = 2-pyrimidine) have been synthesized, the ligands 2 and 5 for the first time. Their ligand properties were probed by the synthesis of gold(I) complexes. Reaction with (tht)AuCl (tht = tetrahydrothiophene) yielded the chlorogold complexes Ph2RP-Au-Cl (R = qn, 6; iqn, 7; pym, 8) and Ph2RAs-Au-Cl (R = qn, 9; iqn, 10) in high yields. Further treatment of 7 and 8 with one equivalent of AgBF4 provided the complexes [(Ph2Piqn)Au]BF4, 11, [(Ph2Ppym)Au]BF4, 12, and [(Ph2Piqn)Au(tht)]BF4, 14. For comparison, the previously reported complex [(Ph2Ppy)Au]BF4 (py = pyridine), 13, was re-investigated. The compounds were characterized by elemental analyses, mass spectrometry and NMR spectroscopy. In addition, the solid-state structures of 2, 3, 6, 7, 9 - 14 have been determined by X-ray crystallography. The chloro-gold compounds crystallize in the common rod-like structure known from R3EAuCl (R = aryl, E = P, As) complexes without further aggregation via aurophilic interactions. In all cases the phosphine acts as a monodentate ligand. In the solid state compounds 11 - 13 feature an unprecedented cyclic trinuclear aggregation pattern, in which the Au(I) atoms are linearly coordinated by the bridging phosphine ligands forming a cyclic (P-Au-N)3 arrangement. The resulting twelvemembered ring is further stabilized by Au · · · Au interactions. Due to the presence of these Au · · · Au contacts, 11 - 13 are emissive in the solid state but not in solution

scholarly journals Temperature and UV light affect the activity of marine cell-free enzymes

2017 ◽  
Vol 14 (17) ◽  
pp. 3971-3977 ◽  
Author(s):  
Blair Thomson ◽  
Christopher David Hepburn ◽  
Miles Lamare ◽  
Federico Baltar
Keyword(s):  
Organic Matter ◽  
Extracellular Enzymes ◽  
Elevated Temperatures ◽  
Uv Light ◽  
Control Mechanisms ◽  
Potential Control ◽  
Control Factors ◽  
Rate Limiting Step ◽  
Ocean Environment ◽  
First Time

Abstract. Microbial extracellular enzymatic activity (EEA) is the rate-limiting step in the degradation of organic matter in the oceans. These extracellular enzymes exist in two forms: cell-bound, which are attached to the microbial cell wall, and cell-free, which are completely free of the cell. Contrary to previous understanding, cell-free extracellular enzymes make up a substantial proportion of the total marine EEA. Little is known about these abundant cell-free enzymes, including what factors control their activity once they are away from their sites (cells). Experiments were run to assess how cell-free enzymes (excluding microbes) respond to ultraviolet radiation (UVR) and temperature manipulations, previously suggested as potential control factors for these enzymes. The experiments were done with New Zealand coastal waters and the enzymes studied were alkaline phosphatase (APase), β-glucosidase, (BGase), and leucine aminopeptidase (LAPase). Environmentally relevant UVR (i.e. in situ UVR levels measured at our site) reduced cell-free enzyme activities by up to 87 % when compared to controls, likely a consequence of photodegradation. This effect of UVR on cell-free enzymes differed depending on the UVR fraction. Ambient levels of UV radiation were shown to reduce the activity of cell-free enzymes for the first time. Elevated temperatures (15 °C) increased the activity of cell-free enzymes by up to 53 % when compared to controls (10 °C), likely by enhancing the catalytic activity of the enzymes. Our results suggest the importance of both UVR and temperature as control mechanisms for cell-free enzymes. Given the projected warming ocean environment and the variable UVR light regime, it is possible that there could be major changes in the cell-free EEA and in the enzymes contribution to organic matter remineralization in the future.

Asymmetric hydrogenation in nanoreactors with encapsulated Rh-MonoPhos catalyst

2015 ◽  
Vol 17 (3) ◽  
pp. 1702-1709 ◽  
Author(s):  
Mingmei Zhong ◽  
Xiaoming Zhang ◽  
Yaopeng Zhao ◽  
Can Li ◽  
Qihua Yang
Keyword(s):  
Catalytic Activity ◽  
Asymmetric Hydrogenation ◽  
Hydrogenation Reactions ◽  
Multicomponent Catalyst

Encapsulated multicomponent catalyst, Rh-MonoPhos, in nanoreactors showed excellent catalytic activity in the asymmetric hydrogenation reactions.

scholarly journals Mass bleaching of soft coral, Sarcophyton spp. in Thailand and the role of temperature and salinity stress

2009 ◽  
Vol 66 (7) ◽  
pp. 1515-1519 ◽  
Author(s):  
Suchana Chavanich ◽  
Voranop Viyakarn ◽  
Thepsuda Loyjiw ◽  
Priyapat Pattaratamrong ◽  
Anchalee Chankong
Keyword(s):  
Salinity Stress ◽  
Soft Coral ◽  
Elevated Temperatures ◽  
Gulf Of Thailand ◽  
Field Observations ◽  
Experimental Trial ◽  
First Time ◽  
Upper Gulf Of Thailand ◽  
Mass Bleaching

Abstract Chavanich, S., Viyakarn, V., Loyjiw, T., Pattaratamrong, P., and Chankong, A. 2009. Mass bleaching of soft coral, Sarcophyton spp. in Thailand and the role of temperature and salinity stress. – ICES Journal of Marine Science, 66: 1515–1519. From June to October 2006 and 2007, mass bleaching of the soft coral, Sarcophyton spp., occurred for the first time in the upper Gulf of Thailand. Approximately 90% of the populations experienced extensive bleaching, and almost 95% of colonies were affected. Field observations also revealed that fragmentation of Sarcophyton spp. set in 1 month after the onset of bleaching. Some colonies started to recover to some extent by the end of July, with 95% of the population of Sarcophyton spp. recovering by October. Both acute and chronic trials were conducted to determine whether temperature and/or salinity triggered bleaching. In the acute tests, Sarcophyton spp. at 40°C and salinity 20 psu were completely bleached, and death occurred after 57 and 204 h, respectively. However, the colonies at 40 psu could survive through the experimental trial. In the chronic tests, Sarcophyton spp. died when exposed to 34°C, whereas complete bleaching and mortality of Sarcophyton spp. occurred at salinities of 10 and 49 psu. We conclude that elevated temperatures had a greater effect on the bleaching of Sarcophyton spp. than did salinity.

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