Use of chiral solvents
in asymmetric synthesis as a sole source
of enantioselection remains largely unexplored in organic synthesis.
We found that the use of a helical macromolecular catalyst of which
helical chirality is dynamically formed in chiral solvents allowed
several mechanistically different reactions to proceed with high enantioselectivity.
In this system, the chirality of the solvent, such as limonene, induces
a configurational imbalance to the helical macromolecular scaffold
of the catalyst, and in turn to the reaction products through palladium-catalyzed
asymmetric reactions including Suzuki-Miyaura cross-coupling (up to
98% ee), styrene hydrosilylation (up to 95% ee), and silaboration
(up to 89% ee). Not only enantiomerically pure limonene but also limonene
with low enantiomeric excesses induce single-handed helical structures
with majority-rule-based amplification of homochirality. The helical
conformation of the macromolecular catalyst was retained even in the
absence of limonene in the solid state, enabling asymmetric cross-coupling
in achiral solvent with high enantioselectivity.
AlGaN-based ultraviolet-A (UVA) light-emitting-diodes (LEDs) at emission under 330 nm are of great importance for numerous applications, including medicine and photochemical technologies. In this Letter, a highly relaxed n-AlGaN electron injection layer (EIL) underneath the multi-quantum wells (MQWs) for the suppression of both threading dislocation densities and piezoelectric effect was attempted. When the Ga-rich n-AlGaN EIL in the UVA LED was relaxed up to 75%, the full width at half-maximum values of the X-ray rocking curves for the (10–12) planes were reduced from our previous value of approximately 793 to 564 arcsec. Subsequently, a maximum light power of 3.1 mW was achieved in the 326 nm band UVA LED. However, carrier confinement and transport issues in the MQWs were observed. To resolve these issues of carrier confinement and transport, we provide a short roadmap for experimental efforts to realize an internal quantum efficiency (IQE) beyond 53% in AlGaN UVA-MQWs.
Poly(quinoxaline-2,3-diyl)s with chiral (S)-2-butoxymethyl side chains dissolved in 1,2-dichloroethane experience a reversible pressure-dependent helix inversion from P- to M-helical structures between 0.1 MPa and 200 MPa.
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