Heterogeneous catalysis with nickel-on-graphite (Ni/Cg):: Reduction of aryl tosylates and mesylates
Heterogeneous catalysis with nickel-on-graphite (Ni/Cg):: Reduction of aryl tosylates and mesylates
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DOI：
10.1002/anie.200502887
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发表时间：
2006-01-01
影响因子：
16.6
通讯作者：
Kogan, V
中科院分区：
文献类型：
--
作者：
Lipshutz, BH;Frieman, BA;Kogan, V
将军反应在氩气气氛下在烘箱干燥的玻璃器皿中用Teflon涂覆的搅拌棒和干燥隔膜进行。使用前，从Na/二苯甲酮基中新鲜蒸馏二氧杂环己烷。使用前，从CaH中新鲜蒸馏DMF。将Ni/Cg储存并在手套箱中称量为黑色粉末。所有市售试剂在使用前在惰性气氛下从CaH 2或分子筛中蒸馏。Ni（NO3）2·。6 H2O和石墨粉（1-2 μm）购自Aldrich。3，4-二甲氧基-6-甲基-2-甲苯磺酰氧基-苯甲醛购自Sarchem Labs。8-羟基喹哪啶、水杨酰苯胺、L-酪氨酸、L-丙氨酸乙酯、6-羟基黄酮、4-羟基苯甲酸甲酯、3 '-羟基苯乙酮和对甲苯磺酰氯购自Acros。除了二肽之外，所有甲苯磺酸酯均由市售酚类制备。使用Personal Chemistry（现为Biotage）Emrys Optimizer和2-5 mL Pyrex反应容器进行所有微波实验，所述反应容器在氩气气氛下火焰干燥，配备有Teflon搅拌棒和Teflon涂覆的反应容器盖。ICP-AES分析是在Thermo Jobyll Ash IRIS等离子体光谱仪上进行的。使用HP-5-毛细管柱（0.25 µm x 30 m;交联的5%PH ME硅氧烷）进行GC分析，时间程序为50 ℃下5 min，然后以20 ℃/min的速度升温至280 ℃，并在该温度下保持20 min。使用Davisil Grade 633 Type 60 A硅胶进行柱色谱。在商业Kieselgel 60 F254硅胶板上进行TLC分析。在Varian Inova系统上使用CDCl 3作为溶剂获得NMR谱，分别在400 MHz和100 MHz下进行质子和碳共振。FTIR光谱在ATI Mattson Infinity系列光谱仪上在纯NaCl板上获得，并以cm-1报告。在VF Autospec或分析型VG-70-250 HF仪器上获得质谱数据。将石墨粉末（3.75 g，1-2 µm）加入到含有搅拌棒的100 mL圆底烧瓶中。将727 mg（Aldrich，24，407 -4，通过ICP测定的Ni含量：92%; 2.30 mmol）Ni（NO3）2·6 H2O在35 mL去离子H2O中的溶液加入到石墨中，并加入40 mL去离子H2O以冲洗烧瓶的侧面。将烧瓶在氩气下吹扫并剧烈搅拌1分钟。将烧瓶浸没在正氩气流下的超声浴中60分钟。然后将烧瓶连接到氩气吹扫的蒸馏装置上并置于搅拌板上的预热的175-180 ℃砂浴中。随着蒸馏结束，烧瓶温度升高
General. Reactions were performed in oven-dried glassware under an argon atmosphere with Teflon coated stir bars and dry septa. Dioxane was freshly distilled from Na/benzophenone ketyl prior to use. DMF was freshly distilled from CaH prior to use. Ni/Cg was stored and weighed out as a black powder in a glove box. All commercially available reagents were distilled either from CaH2 or molecular sieves under an inert atmosphere before use. Ni (NO3) 2•. 6H2O and graphite powder (1-2 µm) were purchased from Aldrich. 3, 4-Dimethyoxy-6-methyl-2-tosyloxy-benzaldehyde was purchased from Sarchem Labs. 8-Hydroxyquinaldine, salicylanilide, L-tyrosine, L-alanine ethyl ester, 6-hydroxyflavone, methyl 4-hydroxybenzoate, 3’-hydroxyacetophenone, and p-toluenesulfonyl chloride were purchased from Acros. All tosylates were prepared from the commercially available phenols except for the dipeptide. All microwave experiments were performed using a Personal Chemistry (now Biotage) Emrys Optimizer and 2-5 mL Pyrex reaction vessels that were flame dried under an argon atmosphere equipped with a Teflon stir bar and Teflon coated reaction vessel cap. ICP-AES analyses was performed on a Thermo Jarrell Ash IRIS plasma spectrometer. GC analyses were performed using an HP-5-capillary column (0.25 µm x 30 m; cross-linked 5% PH ME siloxane) and a time program with 5 min at 50 C followed by 20 C/min ramp to 280 C, and 20 min holding at this temp. Column chromatography was performed using Davisil Grade 633 Type 60A silica gel. TLC analyses was performed on commercial Kieselgel 60 F254 silica gel plates. NMR spectra were obtained on Varian Inova systems using CDCl3 as the solvent with proton and carbon resonance at 400 MHz and 100 MHz, respectively. FTIR spectra were obtained on an ATI Mattson Infinity series spectrometer neat on NaCl plates, and are reported in cm-1. Mass spectral data were acquired on a VF Autospec or an analytical VG-70-250 HF instrument.Preparation of Ni (II)/Cg. Graphite powder (3.75 g, 1-2 µm) was added to a 100 mL round bottom flask containing a stir bar. A solution of 727 mg (Aldrich, 24,407-4, Ni content by ICP determination: 92%; 2.30 mmol) Ni (NO3) 2• 6H2O in 35 mL deionized H2O was added to the graphite, and 40 mL of deionized H2O were added to wash down the sides of the flask. The flask was purged under argon and stirred vigorously for 1 min. The flask was submerged in an ultrasonic bath under a positive argon flow for 60 min. The flask was then attached to an argon purged distillation setup and placed in a pre-heated 175-180 C sand bath over a stir plate. As the distillation ended, the flask temperature rises