Arylation is a fundamental reaction that can be mostly fulfilled by electrophilic aromatic substitution and transition-metal-catalysed aryl functionalization. Although the azo group has been used as a directing group for many transformations via transition-metal-catalysed aryl carbon-hydrogen (C-H) bond activation, there remain significant unmet challenges in organocatalytic arylation. Here, we show that the azo group can effectively act as both a directing and activating group for organocatalytic asymmetric arylation of indoles via formal nucleophilic aromatic substitution of azobenzene derivatives. Thus, a wide range of axially chiral arylindoles have been achieved in good yields with excellent enantioselectivities by utilizing chiral phosphoric acid as catalyst. Furthermore, highly enantioenriched pyrroloindoles bearing two contiguous quaternary chiral centres have also been obtained via a cascade enantioselective formal nucleophilic aromatic substitution-cyclization process. This strategy should be useful in other related research fields and will open new avenues for organocatalytic asymmetric aryl functionalization.
The first phosphoric acid catalyzed direct arylation of 2-naphthylamines with iminoquinones for the atroposelective synthesis of axially chiral biaryl amino alcohols has been developed. This reaction constitutes a highly functional-group-tolerant route for the rapid construction of enantioenriched axially chiral biaryl amino alcohols, and is a rare example of 2-naphthylamines acting as nucleophiles in an organocatalytic enantioselective transformation. Furthermore, the products, which feature various halogen atoms, provide access to structurally diverse axially chiral amino alcohols through further transformations.
The first organocatalytic asymmetric synthesis of a spirooxindole skeleton incorporated with a cyclobutane moiety has been successfully developed on the basis of H-bond-directing dienamine activation. Structurally complex spirocyclobutyl oxindoles, which possess four contiguous stereocenters, including one spiro quaternary center, were obtained in good yields (up to 83%) with excellent β,γ-regioselectivity (>19:1) and stereocontrol (up to >19:1 dr and 97% ee).
A stereoselective [3+2] cycloaddition of isocyanoesters to methyleneindolinones catalyzed by a quinine-based thiourea-tertiary amine has been successfully developed. Just by tuning the protecting groups on substrates, a variety of optically enriched 3,3'-pyrrolidinyl spirooxindole diastereomers could be obtained in excellent enantioselectivities (up to 99% ee).
A new chiral Brønsted acid, generated in situ from a chiral phosphoric acid boron (CPAB) complex and water, was successfully applied to asymmetric indole reduction. This “designer acid catalyst”, which is more acidic than TsOH as suggested by DFT calculations, allows the unprecedented direct asymmetric reduction of C2‐aryl‐substituted N‐unprotected indoles and features good to excellent enantioselectivities with broad functional group tolerance. DFT calculations and mechanistic experiments indicates that this reaction undergoes C3‐protonation and hydride‐transfer processes. Besides, bulky C2‐alkyl‐substituted N‐unprotected indoles are also suitable for this system.
Using active control methods for load mitigation in wind turbines could greatly reduce the cost of per kilowatt hour of wind power. In this work, the combined pitch and trailing edge flap control (CPFC) for load mitigation of wind turbines is investigated. The CPFC includes an individual pitch control (IPC) loop and a trailing edge flap control (TEFC) loop, which are combined by a load frequency division control algorithm. The IPC loop is mainly used to mitigate the low frequency loads, and the TEFC loop is mainly used to mitigate the high frequency loads. The CPFC adopts both an azimuth angle feed-forward and a loads feedback control strategy. The azimuth angle feed-forward control strategy should mitigate the asymmetrical loads caused by observable disturbances. and the loads feedback control strategy should decrease asymmetrical loads by closed loop control. A simulation is carried out on the joint platform of FAST and MATLAB. The simulation results show that the damage equivalent load (DEL) of blade root out-of-plane bending moment is reduced by 53.7% while using CPFC, compared to collective pitch control (CPC); and the standard deviation of blade tip out-of-plane deflection is reduced by 50.2% while using CPFC, compared to CPC. The results demonstrate that the CPFC can mitigate the fatigue loads of wind turbines as anticipated.Energies 2018, 11, 2519 2 of 16 reduced by up to 17% and the extreme loads in certain cases dropped 50% by using a multi-rotational mode IPC (higher harmonics control) [6]. Houtzager found that IPC can significantly reduce the vibrations in the wind turbine structure with considerably less high-frequent control action [7].The TEFC can quickly adjust the aerodynamic properties of the blade by regulating the trailing edge flaps' (TEFs) deflection angle. Gaunaa found that TEFC could reduce 10-14.5% of the fatigue equivalent damage loads (DELs) on the blade root moments in simulations, decrease 50-60% of standard deviation of the lift coefficient in wind tunnel tests, and reduce about 14% of the fatigue loads and 20% of the 1P frequency loads in field tests on the Vestas V27 wind turbine [8][9][10]. Barlas found that the fatigue DELs of flap-wise moments were reduced 54% in simulation by TEFC, and a reduction of 50% is measured in wind tunnel experiments [11]. Zhang and Yu found that the reduction of flap-wise root moments and tip deflections by using TEFC were up to 20.4% and 15.7% for the normal turbulence model (NTM); and up to 15.0% and 11.9% for the extreme turbulence model (ETM) [12,13].Since IPC has the advantage of a wide regulation range and the disadvantage of slow response, IPC is considered more suitable to mitigate low frequency loads. TEFC has the characteristics of fast response and local control capability, which makes it more suitable to mitigate the high frequency loads. It therefore should be beneficial to use IPC and TEFC to complement each other. However, relevant studies combining IPC and TEFC are rarely reported. In this work, the proposed combined pitch and trailing...
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