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Aliphatic allylic amines are found in a great variety of complex and biorelevant molecules. The direct allylic C–H amination of alkenes serves as the most straightforward method toward these motifs. However, use of widely available internal alkenes with aliphatic amines in this transformation remains a synthetic challenge. In particular, palladium catalysis faces the twin challenges of inefficient coordination of Pd(II) to internal alkenes but excessively tight and therefore inhibitory coordination of Pd(II) by basic aliphatic amines. We report a general solution to these problems. The developed protocol, in contrast to a classical Pd(II/0) scenario, operates through a blue light–induced Pd(0/I/II) manifold with mild aryl bromide oxidant. This open-shell approach also enables enantio- and diastereoselective allylic C–H amination.

 

DNA methylation is an evolutionarily conserved epigenetic mechanism essential for transposon silencing and heterochromatin assembly. In plants, DNA methylation widely occurs in the CG, CHG, and CHH (H = A, C, or T) contexts, with the maintenance of CHG methylation mediated by CMT3 chromomethylase. However, how CMT3 interacts with the chromatin environment for faithful maintenance of CHG methylation is unclear. Here we report structure-function characterization of the H3K9me2-directed maintenance of CHG methylation by CMT3 and itsZea maysortholog ZMET2. Base-specific interactions and DNA deformation coordinately underpin the substrate specificity of CMT3 and ZMET2, while a bivalent readout of H3K9me2 and H3K18 allosterically stimulates substrate binding. Disruption of the interaction with DNA or H3K9me2/H3K18 led to loss of CMT3/ZMET2 activity in vitro and impairment of genome-wide CHG methylation in vivo. Together, our study uncovers how the intricate interplay of CMT3, repressive histone marks, and DNA sequence mediates heterochromatic CHG methylation.

 

Abstract. The interaction between storm surge and concurrent precipitation is poorly understood in many coastal regions. This paper investigates the potential compound effects from these two flooding drivers along the coast of China for the first time by using the most comprehensive records of storm surge and precipitation. Statistically significant dependence between flooding drivers exists at the majority of locations that are analysed, but the strength of the correlation varies spatially and temporally and depending on how extreme events are defined. In general, we find higher dependence at the south-eastern tide gauges (TGs) (latitude < 30∘ N) compared to the northern TGs. Seasonal variations in the dependence are also evident. Overall there are more sites with significant dependence in the tropical cyclone (TC) season, especially in the summer. Accounting for past sea level rise further increases the dependence between flooding drivers, and future sea level rise will hence likely lead to an increase in the frequency of compound events. We also find notable differences in the meteorological patterns associated with events where both drivers are extreme versus events where only one driver is extreme. Events with both extreme drivers at south-eastern TG sites are caused by low-pressure systems with similar characteristics across locations, including high precipitable water content (PWC) and strong winds that generate high storm surge. Based on historical disaster damages records of Hong Kong, events with both extreme drivers account for the vast majority of damages and casualties, compared to univariate flooding events, where only one flooding driver occurred. Given the large coastal population and low capacity of drainage systems in many Chinese urban coastal areas, these findings highlight the necessity to incorporate compound flooding and its potential changes in a warming climate into risk assessments, urban planning, and the design of coastal infrastructure and flood defences. 

Abstract Extreme sea levels (ESLs) due to typhoon-induced storm surge threaten the societal security of densely populated coastal China. Uncertainty in extreme value analysis (EVA) for ESL estimation has large implications for coastal communities’ adaptation to natural hazards. Here we evaluate uncertainties in ESL estimation and relevant driving factors based on hourly observations from 13 tide gauge stations and a complementary dataset derived from a hydrodynamic model. Results indicate significant uncertainties in ESL estimations stemming from using different EVA methods, which then propagate to the inundation assessment. Amplification factors due to sea-level rise (SLR) are highly sensitive to local relative SLR and the shape of the exceedance probability curve, which in turn depends on the selected EVA method. The hydrodynamic model hindcast indicates that high ESLs mainly occurred in eastern coastal China due to typhoon-induced storm surge. Larger uncertainties in the modelled ESLs are found for the coasts of the Yangtze River Delta, and particularly in the river mouth region. Future research and adaptation planning should prioritize these regions given expected future rising sea level, compound flood events, and human-induced factors (e.g. subsidence). This study provides theoretical and practical references for adaptation to ESL-related hazards along coastal China, with implications for coastal regions worldwide. 

Structurally complex diazo‐containing scaffolds are formed by conjugate addition to vinyl diazonium salts. The electrophile, a little studied α‐diazonium‐α,β‐unsaturated carbonyl compound, is formed at low temperature under mild conditions by treating β‐hydroxy‐α‐diazo carbonyls with Sc(OTf)₃. Conjugate addition occurs selectively at the 3‐position of indole to give α‐diazo‐β‐indole carbonyls, and enoxy silanes react to give 2‐diazo‐1,4‐dicarbonyl products. These reactions result in the formation of tertiary and quaternary centers, and give products that would be otherwise difficult to form. Importantly, the diazo functional group is retained within the molecule for future manipulation. Treating an α‐diazo ester indole addition product with Rh₂(OAc)₄caused a rearrangement to occur to give a 2‐(1H‐indol‐3‐yl)‐2‐enoate. In the case of diazo ketone compounds, this shift occurred spontaneously on prolonged exposure to the Lewis acidic reaction conditions.

 

Structurally complex diazo‐containing scaffolds are formed by conjugate addition to vinyl diazonium salts. The electrophile, a little studied α‐diazonium‐α,β‐unsaturated carbonyl compound, is formed at low temperature under mild conditions by treating β‐hydroxy‐α‐diazo carbonyls with Sc(OTf)₃. Conjugate addition occurs selectively at the 3‐position of indole to give α‐diazo‐β‐indole carbonyls, and enoxy silanes react to give 2‐diazo‐1,4‐dicarbonyl products. These reactions result in the formation of tertiary and quaternary centers, and give products that would be otherwise difficult to form. Importantly, the diazo functional group is retained within the molecule for future manipulation. Treating an α‐diazo ester indole addition product with Rh₂(OAc)₄caused a rearrangement to occur to give a 2‐(1H‐indol‐3‐yl)‐2‐enoate. In the case of diazo ketone compounds, this shift occurred spontaneously on prolonged exposure to the Lewis acidic reaction conditions.