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91.
黄峰  邓玉澎 《应用光学》2020,41(1):37-42
随着近年来图像传感器的快速商用化以及生物识别算法的发展,虹膜识别功能得以应用于移动终端设备。获取虹膜图像是虹膜识别的关键一步,运用ZEMAX光学设计软件设计了一款适用于手机的虹膜识别镜头。该镜头采用豪威科技公司OmniVision_OV2281传感器,采用三片式非球面光学塑料设计,F数为2.3,全视场角为34°,在1/2奈奎斯特频率220 lp/mm处MTF值均大于0.39,且系统总长仅3 mm。根据ZEMAX像质评价方法以及公差分析结果可知,该镜头各项光学指标优良,具有像质好、体积小,质量轻、价格低、容易加工等特点。  相似文献   
92.
A transition metal free process for conjunctive functionalization of alkenylboron ate-complexes with electrophilic fluoroalkylthiolating reagents is described, affording β-trifluoroalkylthiolated and difluoroalkylthiolated boronic esters in good yield and excellent diastereoselectivity. The potential applicability of the method was demonstrated by the preparation of a difluoromethylthiolated mimic 12 of a potential drug molecule PF-4191834 for the treatment of asthma.

A transition metal free process for conjunctive functionalization of alkenylboron ate-complexes with electrophilic fluoroalkylthiolating reagents affords β-tri- and difluoroalkylthiolated boronic esters in good yield and diastereoselectivity.

An electrophile-induced 1,2-metalate migration of an alkenylboron “ate” complex and subsequent base-promoted β-elimination to form a functionalized cis-alkene, now the so-called Zweifel reaction, was first reported by Zweifel and co-workers in 1967 (Fig. 1A).1–3 The reaction was proposed to proceed via an initial attack of the π electron of the alkene moiety to iodine to generate a zwitterionic iodonium ion, which then undergoes a stereospecific 1,2-metalate to afford a β-iodoboronic ester, followed by anti-elimination upon treatment with a base to afford a cis-olefin. Thus, if the iodine is replaced by an alternative electrophilic reagent and the use of a base is omitted, an interrupted-Zweifel reaction for the preparation of a stereospecific β-functionalized boronic ester could be realized. Toward this end, Aggarwal reported the first example of such a reaction by employing PhSeCl as the electrophilic reagent.4 It was proposed that PhSeCl first reacts with an alkenylboronate complex to form a zwitterionic seleniranium ion. Subsequent diastereospecific 1,2-metalate migration affords the stereospecific β-seleno-alkylboronate (Fig. 1B). Likewise, shortly after, Denmark and co-workers reported an analogous Lewis-base catalysed enantioselective and diastereoselective carbosulfenylation of an alkenylboronate complex using N-arylthiosaccharin as the electrophile (Fig. 1C).5Open in a separate windowFig. 1The interrupted Zweifel reaction.In light of these discoveries and our recent success in the development of a toolbox of electrophilic fluoroalkylthiolating reagents including three trifluoromethylthiolating reagents α-cumyltrifluoromethane sulfenate,6N-trifluoromethylthio-saccharin7 and N-trifluoromethylthiodibenzenesulfonimide,8 and two difluoromethylthiolating reagents N-difluoromethylthiophthalimide9 and S-(difluoromethyl)benzenesulfonothioate,10 we wondered whether these electrophilic fluoroalkylthiolating reagents could also trigger the proposed stereospecific 1,2-metalatation of the alkenylboronate complex to afford β-fluoroalkylthiolated borane derivatives (Fig. 1D). The trifluoromethylthio (–SCF3) and the difluoromethylthio (–SCF2H) groups have gained great attention recently, partially because of their high and tuneable lipophilicity11 that might improve the drug candidate''s cell membrane permeability and consequently, its overall pharmacokinetics.12 Thus, the development of new efficient reactions for the incorporation of the trifluoromethylthio13 or difluoromethylthio groups14 would be of vital importance in facilitating medicinal chemists'' endeavours in new drug discovery. Herein, we report that by employing electrophilic difluoromethylthiolating reagent PhSO2SCF2H 2a as the electrophile, the proposed difluoromethylthiolating induced stereospecific 1,2-metalate migration of alkenyl boronate complexes occurred smoothly to afford β-difluoromethylthiolated boronic esters in good yields and excellent diastereoselectivity. Likewise, when electrophilic trifluoromethylthiolating reagent N-trifluoromethylthiosaccharin 7 was used, an analogous reaction for the diastereoselective formation of β-trifluoromethylthiolated boronic esters was successfully achieved.We began our study by examining the reaction of the electrophilic difluoromethylthiolating reagent 2a with the alkenylboronate complex which was generated in situ by mixing 1a and PhLi in diethyl ether. It was found that the reaction in CH3CN occurred in full conversion after 12 hours at room temperature, affording the corresponding product 3a in 53% yield (Table 1, entry 1). When the amount of PhLi was increased to 1.3 equivalents, the yield was increased to 76%, while the yield decreased to 66% when 2.0 equivalents of PhLi were used, likely due to the decomposition of the product under strong basic conditions (Table 1, entries 1–5). We then further investigated the effect of the reaction temperature and the solvent. It was found that the temperature did not affect the reaction significantly since the yields of the desired products were decreased slightly to 72% and 70%, respectively, when the reactions were conducted at 0 °C or −15 °C (Table 1, entries 6 and 7). Likewise, the reaction was not sensitive to the polarity of the solvent since reactions conducted in less polar solvents such as THF or CH2Cl2 or nonpolar solvents like toluene occurred in slightly lower 60–73% yields (Table 1, entries 9–11). We also found that reaction using N-difluoromethylthiophthalimide as the electrophilic difluoromethylthiolating reagent gave the same product in a slightly lower yield (Table 1, entry 8).Optimization of conditions for the reaction of the alkenyl boronate complex with PhSO2SCF2Ha
EntryEquiv. of PhLiSolventTemp (°C)Yielda (%)
11.0CH3CNrt53
21.1CH3CNrt60
31.2CH3CNrt72
41.3CH3CNrt76(72)b
52.0CH3CNrt66
61.3CH3CN072
71.3CH3CN−1570
81.3CH3CNrt56c
91.3THFrt73
101.3CH2Cl2rt64
111.3Toluenert60
Open in a separate windowaReaction conditions: vinyl boronate 1a (0.10 mmol) and reagent 2a (0.15 mmol), in CH3CN (1.0 mL) at room temperature for 12 h; Yields were determined by 19F NMR spectroscopy using PhCF3 as an internal standard.bIsolated yield.c N-Difluoromethylthiophthalimide was used.With optimum reaction conditions established, a range of different alkenylboronate complexes were tested under standard conditions (Scheme 1). Alkenylboronate complexes obtained by treating 3,6-dihydro-2H-pyran-4-boronic acid pinacol ester with diverse aryl lithiums reacted efficiently with reagent 2a to give the corresponding β-difluoroalkylthionated boronic esters 3b–e and 3g–m in good yield and excellent diastereoselectivity. A range of aryllithiums with both the electron-donating methoxy group (3c) and electron-withdrawing groups such as a fluoride (3d) or a trifluoromethyl group (3g) or a bulky tert-butyl group at meta-position (3i) worked well. The reaction can also proceed smoothly for naphthyllithium (3h) and n-butyllithium (3j). Moreover, organolithiums generated from heteroaromatics, such as indole (3k), benzothiophene (3l), benzofuran (3m), could also be used. Notably, it is well-known that bromine is not compatible with butyl lithium. Yet, 3f with a para-bromophenyl moiety was obtained from the reaction of the alkenylboronate complex in situ generated by treating (3,6-dihydro-2H-pyran-4-yl)lithium with 4-bromophenylboronic acid pinacol ester. However, the alkenylboronate complex generated by treating (E)-4,4,5,5-tetramethyl-2-(5-phenylpent-1-en-1-yl)-1,3,2-dioxaborolane with tert-butyllithium, failed to react with reagent 2a to give the corresponding β-difluoroalkylthionated boronic esters (3r). Next, the scope with respect to the alkenyl boronic ester component was explored. 3,6-Dihydro-2H-thiopyran-4-ylboronic acid pinacol ester (3n), or N-Ts-3,6-dihydro-2H-pyran-4-boronic acid pinacol ester (3o) and 1-phenylvinylboronic acid pinacol ester (3q) could react well to afford the corresponding products. To demonstrate the scalability of the reaction, 3p was prepared on a gram scale in 75% yield. Furthermore, bridged cyclic boronate 3s could also be obtained in moderate yield, and the anti diastereoselectivity of the reaction was confirmed by X-ray diffraction of its single crystals.Open in a separate windowScheme 1Scope of 1,2-metalate migration of alkenyl boronates with reagent 2a.a a Reaction conditions: alkenyl or aryl boronic ester (0.30 mmol, 1.0 equiv.), R3Li (0.33 mmol, 1.1 equiv.) in Et2O (1.5 mL) at −78 °C to room temperature for 30 min; then the solvent was swapped with CH3CN (3.0 mL); 2a (0.45 mmol, 1.5 equiv.) was added. Isolated yield. b R3Li (0.39 mmol) in Et2O (1.5 mL) at 0 °C to room temperature for 30 min. c The mixture was treated with NaBO3 (0.9 mmol, 3.0 equiv.) in THF/H2O (v/v = 1 : 1, 6 mL) at room temperature for 6 h.Furthermore, it was found that the resultant boronic esters could be easily oxidized to alcohols, with the difluoromethylthio group remaining intact, by treatment with 3.0 equivalents of NaBO3 at room temperature for 6 h. For example, difluoromethylthiolated β-alcohols 4a–4d were obtained in moderate to good yields under these conditions (Scheme 1).In general, it is a common practice to use E or Z-alkenes in the reaction to probe whether the reaction is stereo-specific. Thus, we examined the reaction of E-(3′-phenylpropyl)vinyl boronic acid pinacol ester and Z-(3′-phenylpropyl)vinyl boronic acid pinacol ester under standard conditions. It was found that the reaction is stereospecific since the reactions of E- and Z-alkenyl boronic esters specifically produced corresponding anti- and cis-difluoromethylthiolated alcohols (4e and 4f) with excellent diasteroselectivity (>20 : 1), respectively (Scheme 2).Open in a separate windowScheme 2Reactions of E- and Z-alkenyl boronate complexes with reagent 2a.To further expand the scope of the reaction, we studied the difluoromethylthiolative triggered stereospecific 1,2-metalate migration of in situ generated vinyl boronate complexes from enantio-enriched secondary alkyl boronic esters with vinyl lithium. The resulting crude alkyl boronic esters were then sequentially oxidized by NaBO3 and Jone''s oxidation to give α-chiral ketone derivatives. It was found that chirality of the secondary alkyl boronic esters was stereospecifically transferred to the final products 6a–c with 100% es (Scheme 3).Open in a separate windowScheme 3Synthesis of α-chiral ketones by stereospecific 1,2-migration.a a Reaction conditions: alkyl boronic ester (0.30 mmol, 1.0 equiv.), R3Li (0.36 mmol, 1.2 equiv.) in Et2O (1.5 mL) at −78 °C to room temperature for 30 min; then the solvent was swapped with CH3CN (3.0 mL); 2a (0.45 mmol, 1.5 equiv.) was added; and then NaBO3 (0.9 mmol, 3.0 equiv.) in THF/H2O (v/v = 1 : 1, 6 mL) was used; and then Jone''s reagent (0.45 mmol, 1.5 equiv.) was used. Isolated yield.Encouraged by the excellent diastereoselective difluoromethylthiolation of alkenyl boronic acid pinacol esters, we then extended this highly selective reaction to analogous trifluoromethylthiolation triggered 1,2-metalate migration of alkenylboronate (Scheme 4). It was found that when N-trifluoromethylthiosaccharin 7 was used as the electrophilic trifluoromethylthiolating reagent, the reaction of alkenylboronate derived from PhLi occurred smoothly in CH3CN after 12 h at 0 °C to give β-trifluoroalkylthionated boronic ester 8a in 76% yield (8a). Likewise, a variety of other aryllithiums could be successfully employed in this reaction to afford the corresponding β-trifluoroalkylthionated boronic esters (8b–h) in high yields. This reaction appears to be compatible with labile functional groups such as chlorine (8b), trifluoromethyl (8c), ketal (8d), and acetal (8e). In addition, organolithiums generated from heteroaromatics, such as benzofuran (8g) and benzothiophene (8h) could also be employed. Lastly, it was found that a single diastereoisomer with an anti configuration (8i) was isolated in 75% yield when the corresponding E-alkenyl boronic ester was used. Yet, the scope of alkenyoboronate complexes for the reaction with N-trifluoromethylthiosaccharin 7 is not as broad as that with PhSO2SCF2H since alkenylboronate complexes generated by treating 3,6-dihydro-2H-pyran-4-boronic acid pinacol ester with n-butyllithium or by treating 2,2-dimethylethenylboronic acid pinacol ester with lithium benzothiophene failed to produce the desired β-trifluoroalkylthionated boronic esters 8j and 8k under the standard conditions.Open in a separate windowScheme 4Scope of 1,2-metalate migration of alkenyl boronates with electrophilic trifluoromethylthiolating reagent 7.a a Reaction conditions: alkenyl boronic ester (0.30 mmol, 1.0 equiv.), R3Li (0.33 mmol, 1.1 equiv.) in Et2O (1.5 mL) at −78 °C to room temperature for 30 min; then the solvent was swapped with CH3CN (3.0 mL); reagent 5 (0.45 mmol) was added. b R3Li (0.39 mmol, 1.3 equiv.) in Et2O (1.5 mL) at 0 °C to room temperature for 30 min. Isolated yield.To further demonstrate the great potential of this reaction, we applied this protocol as a key step in the synthesis of a difluoromethylthiolated mimic of PF-4191834, which is a potent competitive inhibitor of the 5-lipoxygenase (5 LOX) enzyme for the treatment of mild to moderate asthma15 (Fig. 2). Firstly, arylsulfide 11 was synthesized efficiently by deborylthiolation of organoboron 9 with thiosulfonate 10 in the presence of 5 mol% CuSO4 as the catalyst. Lithium halide exchange of compound 11 with t-butyllithium at −78 °C for 30 min generated the corresponding aryl lithium species in situ, which was treated with 3,6-dihydro-2H-pyran-4-boronic acid pinacol ester to afford the alkenyl boronate complex. Switching the solvent from diether ether to CH3CN, followed by the addition of 1.5 equivalents of PhSO2SCF2H 2a, and further reaction at room temperature for 12 h produced the difluoromethylthiolated mimic of PF-4191834 12 in 70% yield. This example showed the potential of the current protocol in the preparation of biological active compounds.Open in a separate windowFig. 2Construction of PF-4191834 mimic by conjunctive cross-coupling.In summary, a method of conjunctive three-component coupling between alkenyl boronic esters, organolithiums and electrophilic fluoroalkylthiolating reagents was successfully developed, affording β-trifluoroalkylthionated and difluoroalkylthionated boronic esters in good yield and excellent diastereoselectivity. The reaction is stereospecific since the reaction of the E-alkenyl boronic ester specifically gave an anti-difluoromethylthiolated β-alcohol and the reaction of the Z-alkenyl boronic ester specifically gave cis-difluoromethylthiolated β-alcohol 4f with excellent diasteroselectivity (>20 : 1). The potential applicability of the method was demonstrated by the preparation of a difluoromethylthiolated derivative of a potential drug molecule for the treatment of asthma PF-4191834 12. The reactions of the alkenyl boronate complexes with other electrophilic fluoroalkylating reagents are currently actively underway in our laboratory.  相似文献   
93.
巩柯语  张涛  闫雷  高峰  苗洋 《人工晶体学报》2020,49(10):1863-1869
以脱脂棉为原料通过Mg2+模板法获取多孔碳化棉结构,再通过水热法在其表面及内部孔隙负载SnO2颗粒,获得多孔碳化棉与SnO2颗粒的复合材料.利用扫描电子显微镜(SEM)、拉曼光谱、X射线衍射分析(XRD)分析材料的微观形貌,利用循环伏安(CV)和电化学阻抗(EIS)测试评价其作为锂离子电池负极材料的电化学性能.结果表明,通过Mg2+模板法获取负载有SnO2颗粒的多孔碳化棉结构作为负极材料时,在300 mA/g的电流密度下,其容量在100圈后仍维持在500 mAh/g,是一种前景较为理想的锂离子电池负极复合材料.  相似文献   
94.
张颂  魏彪  刘易鑫  毛本将  钱易坤  黄宇晨  冯鹏 《强激光与粒子束》2020,32(5):056001-1-056001-7
研究用于校准场所中子剂量监测仪表的241Am-Be中子参考辐射场计量特性。采用蒙特卡罗方法模拟了空气自由中子参考辐射(FRNR),GB/T 14055规定的最小尺寸中子参考辐射(SRNR)和实际中子参考辐射(ARNR)中不同检验点处中子周围剂量当量率、散射中子占比和能谱分布特征。研究结果表明,空气对FRNR中的剂量率和能谱分布影响小,近似为理想中子参考辐射;采用5%含硼聚乙烯作屏蔽的最小尺寸SRNR可减少热中子,降低散射中子占比,影锥法不适用于小尺寸中子参考辐射中对散射中子的修正;ARNR中的散射中子更少、占比更低,影锥法所得散射中子占比与理论值基本一致。  相似文献   
95.
碳化硅功率MOSFET是宽禁带功率半导体器件的典型代表,具有优异的电气性能。基于低温环境下的应用需求,研究了1200 V碳化硅功率MOSFET在77.7 K至300 K温区的静/动态特性,定性分析了温度对碳化硅功率MOSFET性能的影响。实验结果显示,温度从300 K降低至77.7 K时,阈值电压上升177.24%,漏-源极击穿电压降低32.99%,栅极泄漏电流降低82.51%,导通电阻升高1142.28%,零栅压漏电流降低89.84%(300 K至125 K)。双脉冲测试显示,开通时间增大8.59%,关断时间降低16.86%,开关损耗增加48%。分析发现,碳化硅功率MOSFET较高的界面态密度和较差的沟道迁移率,是导致其在低温下性能劣化的主要原因。  相似文献   
96.
本文通过实验研究了焊锡浸渍、励磁电流PI控制、励磁速率以及励磁幅值对高温超导无绝缘线圈励磁电压特性的影响。实验结果表明:高温超导无绝缘线圈励磁电压具有时延特性,焊锡浸渍、励磁电流PI控制分别会增大和减小时延特性,而励磁速率和励磁幅值不会影响时延特性;励磁电压幅值随励磁速率增大而增大;焊锡浸渍可降低励磁电压幅值,而励磁电流控制对励磁电压幅值影响不明显。  相似文献   
97.
本文使用傅里叶变换微波谱仪研究了乙基苯胺类物质(邻乙基苯胺,间乙基苯胺,对乙基苯胺)的分子结构. 由于此类分子含氮原子(I14N=1),因此跃迁谱线中都呈现出核四级裂分. 通过比较实验测定得到的分子结构,可总结苯胺环上不同位置乙基的取代对氨基及分子整体结构的影响.  相似文献   
98.
采用射频磁控溅射与退火工艺相结合的方法,分别在石英和硒化锌(ZnSe)衬底上制备了掺铪氧化铟(IHfO)薄膜,掺杂比例In2O3∶HfO2为98wt.%∶2wt.%.测试了薄膜的组成结构和3~5μm红外波段的光电性质,分析了退火温度、薄膜厚度和氧气流速对薄膜性能的影响.X射线衍射、扫描电子显微镜和X射线能谱表明,制备的IHfO薄膜具有氧化铟的立方体结构,掺杂铪并没有影响氧化铟的生长方向,但是减小了晶格间距,铪与铟外层电子形成新的杂化轨道.傅里叶变换红外光谱表明,随着退火温度的增加,IHfO薄膜在3~5μm波段的透过率逐渐下降,沉积在ZnSe衬底上的薄膜具有更平稳的透过率,厚度为100nm薄膜在3~5μm波段平均透过率为68%.测试霍尔效应表明,随着氧气流速的增加,IHfO薄膜电阻率逐渐增加,载流子浓度减小,霍尔迁移率变化不明显.晶界散射是影响IHfO薄膜迁移率的主要因素,当氧气流速为0.3sccm时,薄膜最佳电阻率为3.3×10~(-2)Ω·cm.与透可见光波段的导电氧化铟锡(ITO)薄膜相比,制备的IHfO薄膜可以应用在3~5μm红外波段检测气体,红外制导等领域.  相似文献   
99.
By introducing a compatible reducing agent (2‐ethylimidazole) into a mono‐micelle assembly process, we present a type of ordered mesoporous TiO2 microspheres that combines radially aligned mesostructure with Ti3+ defects in mesoporous frameworks. Such reductant acts as a building block of mesostructured frameworks and reduces Ti4+ in situ to generate defects during calcination, giving rise to the coexistence of bulk Ti3+ defects and an ordered mesostructure. The mesoporous TiO2 has both excellent mesoporosity (a high surface area of 106 m2 g?1, a mean pore size of 18.4 nm) and stable defects with an extended photoresponse. Such integration of unique mesoscopic architecture and atomic vacancies provide both effective mass transportation and enhanced light utilization, leading to a remarkable increase in H2 generation rate. A maximum H2 evolution rate of 19.8 mmol g?1 h?1 can be achieved, along with outstanding stability under solar light.  相似文献   
100.
基于大模场面积掺镱光纤搭建了全光纤1030 nm高功率窄线宽光纤激光主振荡功率放大系统,实现了3004 W的最高功率输出,斜率效率69.27%,是目前报道的输出功率最高的1030 nm波段近衍射极限光纤激光器。最高输出功率时,x,y方向的光束质量因子分别为1.169,1.174,3 dB光谱宽度为0.18 nm,放大自发辐射抑制比达到37 dB。  相似文献   
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