Convenient Preparation of Cycloalkenyl Boronic Acid Pinacol Esters

Vivek Rauniyar , Huimin Zhai & Dennis G. Hall
Department of Chemistry, University of Alberta, Edmonton, Alberta, Canada

The Suzuki–Miyaura cross-coupling of aryl or alkenyl boronic acids and esters is one of the most important reactions in organic synthesis,[1] and it has been tremendously utilized in the synthesis of natural products and bioactive molecules.[2] In this context, the analogous cycloalkenyl boronic acids and esters are also important coupling partners to access novel, polysubstituted alkenes. These boronic esters can, however, be forbiddingly expensive. (For example, the 2007 Aldrich price for 1 g of cyclohexenyl boronic acid pinacol ester is CDN$ 285) In general, cycloalkenyl boronates are accessed by Miyaura borylation of cycloalkenyl triflates or halides (Scheme 1).[3] The sensitive cycloalkenyl triflates are in turn obtained from the parent cycloalkanones using deprotonation and enolate quenching with expensive triflating agents.[4] Herein, we report a very convenient preparation and isolation of various cycloalkenyl boronic esters using the Shapiro reaction[5] of cycloalkylhydrazones and isolation of the corresponding cycloalkenyl boronic acids as their pinacol esters. Aside from one example where the organoboron product was not isolated, this appears to be the first report of preparation of cycloalkenyl boronic acid pinacol esters using a Shapiro protocol.[6]

The current methodology provides the requisite cycloalkenyl boronic esters in 65–90% overall yield for a two-step sequence.[7] While working on the modification of the diol scaffold utilized in the 2 SnCl4-catalyzed allylboration of aldehyde substrates (Scheme 2), we noticed that introduction of cycloalkyl groups in the ortho-position of the hydrobenzoin skeleton was crucial for obtaining homoallyl alcohol products in high enantioselectivities.[8] During our optimization efforts to generate various ring sizes on the diol catalyst 2, we required a rapid preparation of the corresponding cycloalkenyl boronic esters. The latter would serve to install various cycloalkyl rings at the ortho-position of the protected hydrobenzoin 1 by a Suzuki–Miyaura cross-coupling process.

A general preparation of cycloalkenyl boronic esters had to be economical and efficient. As such, we envisioned a cycloalkenyl anion capture of a boron-containing electrophile. To this end, we explored a
Shapiro reaction of the cycloalkyl hydrazones to generate cycloalkenyl anions. We anticipated that quenching of the generated anions with commercially available isopropoxy pinacol borate would allow for easier handling and for proper purification and characterization of the products as stable pinacol esters.

In the event, as shown in Scheme 3, cycloalkylhydrazones 4 were readily obtained as crystalline solids in almost quantitative yields by a simple addition=dehydration reaction with inexpensive hydrazide reagent 5 in refluxing absolute ethanol. The majority of cycloalkyl hydrazone substrates started to precipitate out when the reaction reached completion, after which the reaction mixture was cooled in an ice bath to allow for completion of crystallization. The freshly obtained cycloalkyl hydrazones 4 were suspended in hexanes followed by addition of N,Ntetramethylethylenediamine (TMEDA) (3 ml=mmol of hydrazone) and cooled to 78 C. This mixture was treated with 4 equivalents of n- BuLi, after which dinitrogen was extruded at room temperature during 1 to 2 h.

The resulting orange to red-brown solutions containing the corresponding cycloalkenyl anion equivalents were cooled to 78 C and treated with isopropoxypinacol borate 3 (Scheme 3), and the resulting products were easily purified by flash chromatography over silica gel. The resulting cycloalkenyl boronate products 6 are robust and can be stored for weeks without any observable decomposition. Table 1
illustrates the scope of this protocol. The majority of the products were obtained in good to excellent yields, and this chemistry appears to be general for the preparation of various ring sizes of cycloalkenyl
boronic esters from the corresponding cycloalkanones.

CONCLUSION
We have described a two-step sequence that provides easy access to cycloalkenyl boronic esters in good to excellent yields, and this methodology is readily scalable to multigram quantities. The intermediates are robust and can be stored for months without any observable degradation. Accordingly, expensive reagents including palladium catalyst, bis(pinacolato)diboron, and activating agents are avoided. As such, this method should find widespread application in the preparation of cycloalkenylboronic acid pinacol esters and their application in several types of cross-coupling reactions.

EXPERIMENTAL
General
All cycloalkanones were purchased from Aldrich or TCI America. TMEDA was purchased from Acros Organics in 2.5-L containers. Unless otherwise noted, all reactions were performed under an argon atmosphere using flame-dried glassware. TMEDA and hexane were distilled over CaH2. Thin-layer chromatography (TLC) was performed on silica-gel 60 F254 plates and were visualized with UV light and KMnO4 stain. NMR spectra were recorded on 300-, 400-, or 500-MHz instruments. The residual solvent protons (1 H) or the solvent carbons (13C H) were used as internal standards. 1 H NMR data are presented as follows: chemical shift in parts per million downfield from tetramethylsilane (multiplicity, coupling constant, integration). The following abbreviations are used in reporting NMR data: s, singlet; br s, broad singlet; d, doublet; t, triplet; q, quartet; qt, quartet of triplets; dd, doublet of doublets; dt, doublet of triplets; AB, AB quartet; m, multiplet. High-resolution mass spectra were recorded by the University of Alberta Mass Spectrometry Services Laboratory using either electron impact (EI) or electrospray (ES) ionization techniques. Infrared spectra and optical rotations were recorded by the University of Alberta Department of Chemistry Spectral Services.

Compound 4a
p-Tolylsulfonylhydrazine (90.0 g, 0.48 mol) was added to a 250-mL flask equipped with a magnetic stirbar, and this white solid was suspended in 60 ml of absolute ethanol. Cyclopentanone (40.7 g, 0.48 mol) was added to this suspension, and the reaction mixture was heated to reflux at 100 C. After heating for 20 min, the mixture dissolved, and after another 20 min, a white solid corresponding to the hydrazone started crashing out. After heating for 1 h, the reaction mixture was cooled using an ice-water bath to precipitate out the majority of the hydrazone. The resulting solid was collected by filtration and was washed thoroughly with ice-cold ethanol. Air drying under reduced pressure for 1 h afforded 114 g of the required hydrazone in near quantitative yield as a white solid with identical spectral properties compared to literature.[9]
 

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(R)-tert-Butyl 3-aminoazepane-1-carboxylate Catalog No.:AA0032BR CAS No.:1032684-85-7 MDL No.:MFCD11041391 MF:C11H22N2O2 MW:214.3046	trans-4-Cyclohexyl-L-proline Catalog No.:AA00386Z CAS No.:103201-78-1 MDL No.:MFCD08061929 MF:C11H19NO2 MW:197.2741
11,14-Eicosadienoicacid, ethyl ester, (11Z,14Z)- Catalog No.:AA00386Y CAS No.:103213-62-3 MDL No.:MFCD27978909 MF:C22H40O2 MW:336.5518	Fmoc-Cys(Trt)-OH Catalog No.:AA0038A7 CAS No.:103213-32-7 MDL No.:MFCD00038538 MF:C37H31NO4S MW:585.7113
3-(2-Chloropyrimidin-4-yl)-1-methyl-1H-indole Catalog No.:AA003967 CAS No.:1032452-86-0 MDL No.:MFCD26397861 MF:C13H10ClN3 MW:243.6916	2-Amino-N-[2,3-dihydro-7-methoxy-8-[3-(4-morpholinyl)propoxy]imidazo[1,2-c]quinazolin-5-yl]-5-pyrimidinecarboxamide Catalog No.:AA0039IF CAS No.:1032568-63-0 MDL No.:MFCD18633201 MF:C23H28N8O4 MW:480.5196
1-(Pyrimidin-5-yl)ethanone Catalog No.:AA003CYW CAS No.:10325-70-9 MDL No.:MFCD09038477 MF:C6H6N2O MW:122.1246	2-Bromo-3-chlorobenzonitrile Catalog No.:AA003GJW CAS No.:1031929-33-5 MDL No.:MFCD10699544 MF:C7H3BrClN MW:216.4624
2-chloro-5-nitropyrimidine Catalog No.:AA003GWV CAS No.:10320-42-0 MDL No.:MFCD04117995 MF:C4H2ClN3O2 MW:159.5306	3-Bromo-2-fluoro-5-(trifluoromethyl)pyridine Catalog No.:AA003IXM CAS No.:1031929-01-7 MDL No.:MFCD08061304 MF:C6H2BrF4N MW:243.9844
4-Acetamido-2-methylbenzoic acid Catalog No.:AA003KJ8 CAS No.:103204-69-9 MDL No.:MFCD02258874 MF:C10H11NO3 MW:193.1992	4-Methoxy-1H-indole-2-carboxylic acid Catalog No.:AA003LL0 CAS No.:103260-65-7 MDL No.:MFCD02664458 MF:C10H9NO3 MW:191.1834
4-Methylpent-2-enoic acid Catalog No.:AA003LNK CAS No.:10321-71-8 MDL No.:MFCD00043804 MF:C6H10O2 MW:114.1424	Barium chloride dihydrate Catalog No.:AA003NW6 CAS No.:10326-27-9 MDL No.:MFCD00003445 MF:BaCl2H4O2 MW:244.2636
Cadmium diperchlorate hexahydrate Catalog No.:AA003OKC CAS No.:10326-28-0 MDL No.:MFCD00150202 MF:CdCl2H12O14 MW:419.4039	(R)-2-Hydroxypropanoic acid Catalog No.:AA003P4R CAS No.:10326-41-7 MDL No.:MFCD00068311 MF:C3H6O3 MW:90.0779
H-DL-Cys.HCl Catalog No.:AA003PQY CAS No.:10318-18-0 MDL No.:MFCD00064552 MF:C3H7ClNO2S MW:157.6191	PERFLUORO(4-METHYLPENT-2-ENOIC ACID) Catalog No.:AA003TJV CAS No.:103229-89-6 MDL No.:MFCD00153286 MF:C6HF9O2 MW:276.0566
3,5-Dichloro-1H-1,2,4-triazole Catalog No.:AA007HJA CAS No.:10327-87-4 MDL No.:MFCD01421959 MF:C2HCl2N3 MW:137.9554	Ethyl 2-(tetrahydro-2H-pyran-4-yl)acetate Catalog No.:AA007HJL CAS No.:103260-44-2 MDL No.:MFCD03788560 MF:C9H16O3 MW:172.2215
tert-Butyl (1-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)cyclobutyl)carbamate Catalog No.:AA007HJT CAS No.:1032528-06-5 MDL No.:MFCD18762017 MF:C21H32BNO4 MW:373.2941	(2,3-Dihydrobenzofuran-5-yl)methanol Catalog No.:AA007HJJ CAS No.:103262-35-7 MDL No.:MFCD02169755 MF:C9H10O2 MW:150.1745
4-Methyl-2-phenylpyrimidine-5-carboxylic acid Catalog No.:AA007HJV CAS No.:103249-79-2 MDL No.:MFCD02682018 MF:C12H10N2O2 MW:214.2200	Gly-Pro p-nitroanilide hydrochloride Catalog No.:AA007HRO CAS No.:103213-34-9 MDL No.:MFCD00058170 MF:C14H17N3O4 MW:291.3025
2-bromo-3,3,3-trifluoro-1-(4-methylpiperazin-1-yl)propan-1-one Catalog No.:AA007HUH CAS No.:1031927-96-4 MDL No.:MFCD09997950 MF:C8H12BrF3N2O MW:289.0929	Methyl 2-bromo-5-cyanobenzoate Catalog No.:AA007HUI CAS No.:1031927-03-3 MDL No.:MFCD11035757 MF:C9H6BrNO2 MW:240.0534
Guanylyl(2' 5')adenosine ammonium salt Catalog No.:AA007HUK CAS No.:103192-47-8 MDL No.:MFCD00058654 MF:C20H28N11O11P MW:629.4772	2-Bromo-4-(tert-butyl)aniline Catalog No.:AA007XS2 CAS No.:103273-01-4 MDL No.:MFCD00052693 MF:C10H14BrN MW:228.1289
7-Bromo-4-chloro-5H-pyrrolo[3,2-d]pyrimidine Catalog No.:AA007XTS CAS No.:1032650-41-1 MDL No.:MFCD11518977 MF:C6H3BrClN3 MW:232.4651	2-methyl-4-oxo-4,5,6,7-tetrahydro-1-benzofuran-3-carboxylic acid Catalog No.:AA007XUK CAS No.:103204-90-6 MDL No.:MFCD11156801 MF:C10H10O4 MW:194.1840
(3-Bromo-2-cyanophenyl)boronic acid Catalog No.:AA007XUC CAS No.:1032231-32-5 MDL No.:MFCD10696672 MF:C7H5BBrNO2 MW:225.8351	1-Phenyl-2,5-dihydro-1H-pyrrole Catalog No.:AA007XUM CAS No.:103204-12-2 MDL No.:MFCD00091069 MF:C10H11N MW:145.2010
2-(2-oxo-2-phenylethyl)-1H-isoindole-1,3(2H)-dione Catalog No.:AA007XTP CAS No.:1032-67-3 MDL No.:MFCD00086336 MF:C16H11NO3 MW:265.2634	D-Arabinose Catalog No.:AA007XU9 CAS No.:10323-20-3 MDL No.:MFCD00135608 MF:C5H10O5 MW:150.1299
tert-Butyl 1-oxo-2,7-diazaspiro[3.5]nonane-7-carboxylate Catalog No.:AA007XUG CAS No.:1032158-48-7 MDL No.:MFCD12198504 MF:C12H20N2O3 MW:240.2988	Benzoic acid, 4-cyano-2-methyl-, methyl ester Catalog No.:AA007XTW CAS No.:103261-67-2 MDL No.:MFCD18399110 MF:C10H9NO2 MW:175.1840
4-Fluoro-2-iodobenzonitrile Catalog No.:AA007XVL CAS No.:1031929-20-0 MDL No.:MFCD09998181 MF:C7H3FIN MW:247.0083	tert-Butyl 1,9-diazaspiro[5.5]undecane-9-carboxylate Catalog No.:AA007XZ6 CAS No.:1031927-14-6 MDL No.:MFCD09998745 MF:C14H26N2O2 MW:254.3684
(2,5-Dibromopyridin-4-yl)boronic acid Catalog No.:AA007XZD CAS No.:1031843-77-2 MDL No.:MFCD11109338 MF:C5H4BBr2NO2 MW:280.7098	2'-Deoxycytidine-5'-monophosphoric acid Catalog No.:AA0085U0 CAS No.:1032-65-1 MDL No.:MFCD00149428 MF:C9H14N3O7P MW:307.1971
Methyl 5-cyano-2-methylbenzoate Catalog No.:AA0085U6 CAS No.:103261-68-3 MDL No.:MFCD18399111 MF:C10H9NO2 MW:175.1840	2-Bromo-5-iodobenzaldehyde Catalog No.:AA0085UX CAS No.:1032231-24-5 MDL No.:MFCD07779027 MF:C7H4BrIO MW:310.9145
Oxociprofloxacin Catalog No.:AA0085UR CAS No.:103237-52-1 MDL No.:MFCD04973643 MF:C17H16FN3O4 MW:345.3250	tert-Butyl 1-(4-cyanophenyl)cyclobutylcarbamate Catalog No.:AA0085US CAS No.:1032349-97-5 MDL No.:MFCD15071414 MF:C16H20N2O2 MW:272.3422
Chroman-6-carboxylic acid Catalog No.:AA0085VA CAS No.:103203-84-5 MDL No.:MFCD30292879 MF:C10H10O3 MW:178.1846	3-BUtyl-1h-1,2,4-triazol-5-amine Catalog No.:AA0085V7 CAS No.:103205-70-5 MDL No.:MFCD07366087 MF:C6H12N4 MW:140.1863
A939572 Catalog No.:AA0085UY CAS No.:1032229-33-6 MDL No.:MFCD10698997 MF:C20H22ClN3O3 MW:387.8600	(3R,7aS)-3-Phenyltetrahydropyrrolo[1,2-c]oxazol-5(3H)-one Catalog No.:AA0085VC CAS No.:103201-79-2 MDL No.:MFCD02179180 MF:C12H13NO2 MW:203.2371
6-Fluoro-2-hydroxy-3-phenylquinoline Catalog No.:AA0085VX CAS No.:1031928-37-6 MDL No.:MFCD09997959 MF:C15H10FNO MW:239.2444	3-(Allyloxy)benzoic acid Catalog No.:AA0085VB CAS No.:103203-83-4 MDL No.:MFCD00527900 MF:C10H10O3 MW:178.1846
4-Borono-3,5-difluorobenzoic acid Catalog No.:AA0085WF CAS No.:1031857-98-3 MDL No.:MFCD07786257 MF:C7H5BF2O4 MW:201.9200	2,8-Bis(trifluoromethyl)-4-vinylquinoline Catalog No.:AA0085VV CAS No.:1031928-53-6 MDL No.:MFCD10703428 MF:C13H7F6N MW:291.1918
D-Fructose-1,6-diphoshate calcium salt Catalog No.:AA008R66 CAS No.:103213-33-8 MDL No.:MFCD00135874 MF:C6H12CaO12P2 MW:378.1778	L-Glutathione, oxidized (sodium salt) Catalog No.:AA008RGI CAS No.:103239-24-3 MDL No.:MFCD00148894 MF:C20H30N6Na2O12S2 MW:656.5947
3-Methylpyridine-4-boronic acid pinacol ester Catalog No.:AA008RST CAS No.:1032358-00-1 MDL No.:MFCD07374972 MF:C12H18BNO2 MW:219.0878	4-(2-Methoxyphenoxy)benzoic acid Catalog No.:AA008RVE CAS No.:103203-54-9 MDL No.:MFCD01570262 MF:C14H12O4 MW:244.2427
1-Benzyl-2-ethylpiperazine Catalog No.:AA008RY7 CAS No.:1031926-99-4 MDL No.:MFCD07367738 MF:C13H20N2 MW:204.3113	2,3-Dihydro-2-methyl-5-benzofurancarboxylic acid Catalog No.:AA008S8R CAS No.:103204-80-4 MDL No.:MFCD03110444 MF:C10H10O3 MW:178.1846
(3-(Piperidin-1-ylmethyl)phenyl)boronic acid Catalog No.:AA008SRH CAS No.:1032610-59-5 MDL No.:MFCD08060620 MF:C12H18BNO2 MW:219.0878	5-Bromo-2-cyanophenylboronic acid Catalog No.:AA008SRF CAS No.:1032231-30-3 MDL No.:MFCD10696674 MF:C7H5BBrNO2 MW:225.8351
MK-2206 Dihydrochloride Catalog No.:AA008TF8 CAS No.:1032350-13-2 MDL No.:MFCD14584463 MF:C25H23Cl2N5O MW:480.3890	tert-Butyl (1-(4-bromophenyl)cyclobutyl)carbamate Catalog No.:AA008TH6 CAS No.:1032350-06-3 MDL No.:MFCD18072661 MF:C15H20BrNO2 MW:326.2288
Endoxifen HCl Catalog No.:AA008TJ3 CAS No.:1032008-74-4 MDL No.:MFCD16875406 MF:C25H28ClNO2 MW:409.9483	4-(Imidazo[1,2-a]pyrazin-2-yl)-1,2,5-oxadiazol-3-amine Catalog No.:AA008TPL CAS No.:1031927-02-2 MDL No.:MFCD11035755 MF:C8H6N6O MW:202.1728
6-Bromo-3-hydroxyisoquinoline Catalog No.:AA008TTI CAS No.:1031927-91-9 MDL No.:MFCD11110423 MF:C9H6BrNO MW:224.0540	4-Bromo-2-(tert-butyl)phenol Catalog No.:AA008U6H CAS No.:10323-39-4 MDL No.:MFCD00192645 MF:C10H13BrO MW:229.1136
3-METHYL-2,3-DIHYDRO-1,4-BENZODIOXINE-2-CARBOXYLIC ACID Catalog No.:AA008U6W CAS No.:103204-87-1 MDL No.:MFCD03069072 MF:C10H10O4 MW:194.1840	3-(2-Carbamoylphenoxy)propanoic acid Catalog No.:AA008UFJ CAS No.:103204-34-8 MDL No.:MFCD02364319 MF:C10H11NO4 MW:209.1986
Disodium ((2R,3S,5R)-5-(5-fluoro-2,4-dioxo-3,4-dihydropyrimidin-1(2H)-yl)-3-hydroxytetrahydrofuran-2-yl)methyl phosphate Catalog No.:AA008UHC CAS No.:103226-10-4 MDL No.:MFCD16714828 MF:C9H10FN2Na2O8P MW:370.1360	N-(3-Acetyl-2-hydroxyphenyl)acetamide Catalog No.:AA008UXX CAS No.:103205-33-0 MDL No.:MFCD17170001 MF:C10H11NO3 MW:193.1992
(E)-Hept-5-en-3-yn-1-ol Catalog No.:AA008V98 CAS No.:103197-98-4 MDL No.:MFCD16710299 MF:C7H10O MW:110.1537	tert-Butyl (2-(morpholin-2-yl)ethyl)carbamate Catalog No.:AA008VHH CAS No.:1032507-63-3 MDL No.:MFCD09701685 MF:C11H22N2O3 MW:230.3040
3-(Dimethylamino)-1-(naphthalen-1-yl)propan-1-one Catalog No.:AA008X81 CAS No.:10320-49-7 MDL No.:MFCD09753763 MF:C15H17NO MW:227.3016	(R)-Methyl 3-aminobutanoate Catalog No.:AA008XGU CAS No.:103189-63-5 MDL No.:MFCD08058803 MF:C5H11NO2 MW:117.1463
5-Acetamido-2-methylbenzoic acid Catalog No.:AA008YQ9 CAS No.:103204-70-2 MDL No.:MFCD09260822 MF:C10H11NO3 MW:193.1992	5-Bromo-2-cyanobenzoic acid Catalog No.:AA008YY7 CAS No.:1032231-28-9 MDL No.:MFCD15523585 MF:C8H4BrNO2 MW:226.0269
2-(3-Hydroxy-4-methylphenyl)acetic acid Catalog No.:AA008ZYK CAS No.:103262-83-5 MDL No.:MFCD05863285 MF:C9H10O3 MW:166.1739	2,6-Dibromo-3-iodopyridine Catalog No.:AA0090VA CAS No.:1032582-80-1 MDL No.:MFCD13185520 MF:C5H2Br2IN MW:362.7886
3-Amino-1-methyl-1H-indazol-6-ol Catalog No.:AA0090VT CAS No.:1031876-62-6 MDL No.:MFCD11847082 MF:C8H9N3O MW:163.1766	4-Bromo-3-chlorobenzenesulfonamide Catalog No.:AA0090XI CAS No.:1032507-45-1 MDL No.:MFCD09800660 MF:C6H5BrClNO2S MW:270.5314
3-(1,1-Difluoroethyl)benzaldehyde Catalog No.:AA0091JT CAS No.:1032527-37-9 MDL No.:MFCD20527725 MF:C9H8F2O MW:170.1560	Ethyl benzo[d]thiazole-5-carboxylate Catalog No.:AA0091ZH CAS No.:103261-70-7 MDL No.:MFCD13176733 MF:C10H9NO2S MW:207.2490
(S)-2-((((9H-Fluoren-9-yl)methoxy)carbonyl)amino)-3-(2,4-difluorophenyl)propanoic acid Catalog No.:AA009204 CAS No.:1032337-49-7 MDL No.:MFCD07371998 MF:C24H19F2NO4 MW:423.4088	1-(n-Butyl)-4-methylpiperidine Catalog No.:AA0090K7 CAS No.:103199-83-3 MDL No.:MFCD00089157 MF:C10H21N MW:155.2804
tert-Butyl 2-oxo-1,9-diazaspiro[5.5]undecane-9-carboxylate Catalog No.:AA0092Q6 CAS No.:1031927-12-4 MDL No.:MFCD09998742 MF:C14H24N2O3 MW:268.3520	2-Chloro-6-ethoxy-3-phenylquinoline Catalog No.:AA0092YG CAS No.:1031928-18-3 MDL No.:MFCD09998012 MF:C17H14ClNO MW:283.7522
7-Bromo-3-hydroxyquinoline-4-carboxylic acid Catalog No.:AA0093F3 CAS No.:1031929-53-9 MDL No.:MFCD10703487 MF:C10H6BrNO3 MW:268.0635	9-(1,1-Dimethylethyl) 3-[[(1,1-dimethylethoxy)carbonyl]amino]-1,2,3,4-tetrahydro-9H-carbazole-3,9-dicarboxylate Catalog No.:AA009473 CAS No.:1031927-09-9 MDL No.:MFCD09264203 MF:C23H30N2O6 MW:430.4941
N-[(1R,2R)-1-[(Acetyloxy)methyl]-2-hydroxy-2-(4-nitrophenyl)ethyl]-2,2-dichloroacetamide Catalog No.:AA0094AZ CAS No.:10318-16-8 MDL No.:MFCD28898459 MF:C13H14Cl2N2O6 MW:365.1661	tert-Butyl 1-oxo-2,3-dihydro- 1H-spiro[isoquinoline-4,4'-piperidine]-1'-carboxylate Catalog No.:AA0095E6 CAS No.:1032143-15-9 MDL No.:MFCD11227133 MF:C18H24N2O3 MW:316.3948
2-((3-Hydroxyadamantan-1-yl)amino)acetic acid Catalog No.:AA0095JC CAS No.:1032564-18-3 MDL No.:MFCD20278233 MF:C12H19NO3 MW:225.2842	ethyl 5-aMino-1H-pyrazole-4-carboxylate Catalog No.:AA0095XH CAS No.:103259-35-4 MDL No.:MFCD00114562 MF:C6H9N3O2 MW:155.1546
tert-Butyl 2'-oxo-2',3'-dihydro-1'H-spiro[piperidine-4,4'-quinoline]-1-carboxylate Catalog No.:AA0096ET CAS No.:1032143-13-7 MDL No.:MFCD15530225 MF:C18H24N2O3 MW:316.3948	3-Bromo-4-(tert-butyl)aniline Catalog No.:AA0096KU CAS No.:103275-21-4 MDL No.:MFCD09966047 MF:C10H14BrN MW:228.1289
1-(1,1-Difluoroethyl)-2-iodobenzene (stabilized over potassium carbonate) Catalog No.:AA00977R CAS No.:1032507-55-3 MDL No.:MFCD10000931 MF:C8H7F2I MW:268.0425	Cyanine5 NHS ester Catalog No.:AA0097CK CAS No.:1032678-42-4 MDL No.:MFCD32206155 MF:C36H42ClN3O4 MW:616.1894
Cyanine3 NHS ester Catalog No.:AA0097CJ CAS No.:1032678-38-8 MDL No.:MFCD28505569 MF:C34H40ClN3O4 MW:590.1521	4-(4-bromophenyl)azetidin-2-one Catalog No.:AA009LY3 CAS No.:103247-89-8 MDL No.:MFCD11849068 MF:C9H8BrNO MW:226.0699
3-acetamido-2-methylbenzoic acid Catalog No.:AA009SBY CAS No.:103204-68-8 MDL No.:MFCD11844217 MF:C10H11NO3 MW:193.1992	D-2-Amino-1,1,1-trifluoro-3-(methyl)butane Catalog No.:AA00H9XD CAS No.:1032181-63-7 MDL No.:MFCD04972667 MF:C5H10F3N MW:141.1348
1-(3-methylbutanoyl)piperidine-2-carboxylic acid Catalog No.:AA00H9X6 CAS No.:1032056-84-0 MDL No.:MFCD08444769 MF:C11H19NO3 MW:213.2735	(R)-1-(4-Ethylphenyl)ethanamine hydrochloride Catalog No.:AA00H9XA CAS No.:1032149-84-0 MDL No.:MFCD16294244 MF:C10H16ClN MW:185.6937
Ethyl 4-iodo-3-methylbenzoate Catalog No.:AA00H9X5 CAS No.:103204-07-5 MDL No.:MFCD12923263 MF:C10H11IO2 MW:290.0976	N-[(9H-Fluoren-9-ylmethoxy)carbonyl]-3,5-diiodo-L-tyrosine Catalog No.:AA00H9X9 CAS No.:103213-31-6 MDL No.:MFCD00063330 MF:C24H19I2NO5 MW:655.2203
6-Bromo-8-nitroimidazo[1,2-a]pyridine Catalog No.:AA00H9WW CAS No.:1031927-16-8 MDL No.:MFCD09836167 MF:C7H4BrN3O2 MW:242.0296	Ethyl 2-amino-5-bromo-3-methylbenzoate Catalog No.:AA00H9XR CAS No.:1032668-56-6 MDL No.:MFCD12159932 MF:C10H12BrNO2 MW:258.1118
4-(2,5-Dimethyl-1H-pyrrol-1-yl)piperidine Catalog No.:AA00H9XF CAS No.:1032289-55-6 MDL No.:MFCD11858457 MF:C11H18N2 MW:178.2740	1-(3-Chloro-4-methylphenyl)imidazolidin-2-one Catalog No.:AA00H9WX CAS No.:1031927-20-4 MDL No.:MFCD09998747 MF:C10H11ClN2O MW:210.6601
3-[2-(2,5-dimethyl-1H-pyrrol-1-yl)-3-thienyl]-1H-pyrazol-5-amine Catalog No.:AA00INRA CAS No.:1032098-46-6 MDL No.:MFCD07021338 MF:C13H14N4S MW:258.3421	1-[2-nitrodibenzo[b,f][1,4]oxazepin-10(11H)-yl]-1-ethanone Catalog No.:AA00IX10 CAS No.:103248-97-1 MDL No.:MFCD05669955 MF:C15H12N2O4 MW:284.2668
7-(3-chlorophenyl)-3H,4H-thieno[3,2-d]pyrimidin-4-one Catalog No.:AA00J0JW CAS No.:1031969-45-5 MDL No.:MFCD16639689 MF:C12H7ClN2OS MW:262.7148	6-fluoro-1-methyl-7-(4-methylpiperidin-1-yl)-4-oxo-1,4-dihydroquinoline-3-carboxylic acid Catalog No.:AA00J0K2 CAS No.:1031989-25-9 MDL No.:MFCD14729053 MF:C17H19FN2O3 MW:318.3428
4-[(2-thienylmethyl)amino]quinazolin-2(1H)-one Catalog No.:AA00J0MN CAS No.:1031970-30-5 MDL No.:MFCD14729149 MF:C13H11N3OS MW:257.3109	7-(3-methylphenyl)-3H,4H-thieno[3,2-d]pyrimidin-4-one Catalog No.:AA00J0PI CAS No.:1031989-23-7 MDL No.:MFCD16639687 MF:C13H10N2OS MW:242.2963
N-(4-chlorobenzyl)-1-propanamine hydrochloride Catalog No.:AA00J1JY CAS No.:103275-32-7 MDL No.:MFCD07106958 MF:C10H15Cl2N MW:220.1388	N-(2-chlorobenzyl)-2-propanamine hydrochloride Catalog No.:AA00J1L8 CAS No.:103275-31-6 MDL No.:MFCD08559381 MF:C10H15Cl2N MW:220.1388
7-benzyl-2-(4-methylphenyl)-3H,4H,5H,6H,7H,8H-pyrido[3,4-d]pyrimidin-4-one Catalog No.:AA00J7IW CAS No.:1031990-66-5 MDL No.:MFCD14729817 MF:C21H21N3O MW:331.4109	Methyl 2-amino-5-cyano-3-methylbenzoate Catalog No.:AA019ERF CAS No.:1032667-87-0 MDL No.:MFCD20697055 MF:C10H10N2O2 MW:190.1986
Ethyl amino(3,5-dimethyl-1-[3-(trifluoromethyl)phenyl]-1h-pyrazol-4-yl)acetate hydrochloride Catalog No.:AA019K2X CAS No.:1032298-75-1 MDL No.:MFCD08457599 MF:C16H19ClF3N3O2 MW:377.7892	6-(2-fluorobenzyl)-5-oxothiomorpholine-3-carboxylic acid Catalog No.:AA019KD8 CAS No.:1032056-52-2 MDL No.:MFCD09040410 MF:C12H12FNO3S MW:269.2920
1-(thiophene-2-carbonyl)piperidine-2-carboxylic acid Catalog No.:AA019KLI CAS No.:1032056-92-0 MDL No.:MFCD08444841 MF:C11H13NO3S MW:239.2908	2-bromo-4,5-Dimethoxyphenethylamine (hydrochloride) Catalog No.:AA019L34 CAS No.:103275-23-6 MDL No.:MFCD07352307 MF:C10H15BrClNO2 MW:296.5886
5-(4-aminophenyl)-5-methylimidazolidine-2,4-dione Catalog No.:AA019MFS CAS No.:103273-09-2 MDL No.:MFCD10686888 MF:C10H11N3O2 MW:205.2132	5-Amino-3-morpholin-4-yl-1h-pyrazole-4-carbonitrile Catalog No.:AA019OCG CAS No.:103184-16-3 MDL No.:MFCD02071509 MF:C8H11N5O MW:193.2058
4-methanesulfonyl-2-[(2-methoxyphenyl)formamido]butanoic acid Catalog No.:AA019P8J CAS No.:1032039-85-2 MDL No.:MFCD08691093 MF:C13H17NO6S MW:315.3422	2-[(4-tert-Butylbenzoyl)amino]-4-(methylsulfonyl)butanoic acid Catalog No.:AA019P8K CAS No.:1032040-46-2 MDL No.:MFCD09040348 MF:C16H23NO5S MW:341.4225
5-(3-Aminophenyl)-5-methylimidazolidine-2,4-dione Catalog No.:AA019U5S CAS No.:103274-15-3 MDL No.:MFCD11505639 MF:C10H11N3O2 MW:205.2132	1-(prop-2-yn-1-yl)piperidine-2-carboxylic acid Catalog No.:AA019UYV CAS No.:1032056-99-7 MDL No.:MFCD08444860 MF:C9H13NO2 MW:167.2050
6-Fluoro-N,N-dimethylpyridine-3-carboxamide Catalog No.:AA01A4MS CAS No.:1032251-82-3 MDL No.:MFCD19623921 MF:C8H9FN2O MW:168.1683	2-Cyclohexylpropan-1-amine Catalog No.:AA01A7EF CAS No.:103254-49-5 MDL No.:MFCD11590410 MF:C9H19N MW:141.2539
5-(2-Phenylpropan-2-yl)-1,3,4-thiadiazol-2-amine Catalog No.:AA01AB5A CAS No.:1032463-93-6 MDL No.:MFCD12104390 MF:C11H13N3S MW:219.3060	1-(oxolane-2-carbonyl)piperidine-2-carboxylic acid Catalog No.:AA01ABCP CAS No.:1032057-02-5 MDL No.:MFCD08444914 MF:C11H17NO4 MW:227.2570
1-(2-methylcyclopropanecarbonyl)piperidine-2-carboxylic acid Catalog No.:AA01AGK8 CAS No.:1032056-94-2 MDL No.:MFCD08444856 MF:C11H17NO3 MW:211.2576	2-(2-Acetamidophenyl)acetic acid Catalog No.:AA01AGYI CAS No.:103205-34-1 MDL No.:MFCD00229475 MF:C10H11NO3 MW:193.1992
ethyl 2-amino-5-bromo-3-chlorobenzoate Catalog No.:AA01AJE0 CAS No.:1032668-64-6 MDL No.:MFCD12159924 MF:C9H9BrClNO2 MW:278.5303	Methyl 2-ethyl-5-nitrobenzoate Catalog No.:AA01AKZS CAS No.:103205-48-7 MDL No.:MFCD24123502 MF:C10H11NO4 MW:209.1986
5-Amino-1-(3-methylphenyl)-1H-1,2,3-triazole-4-carboxamide Catalog No.:AA01AQH3 CAS No.:103274-40-4 MDL No.:MFCD16653073 MF:C10H11N5O MW:217.2272	6-Chloro-3-pyridin-4-yl[1,2,4]triazolo[4,3-b]pyridazine Catalog No.:AA01ARF4 CAS No.:1032705-69-3 MDL No.:MFCD11042741 MF:C10H6ClN5 MW:231.6411
3-Fluoro-2-methylbenzenesulfonamide Catalog No.:AA01B2V3 CAS No.:1032507-33-7 MDL No.:MFCD09800669 MF:C7H8FNO2S MW:189.2073	1-Benzyl-1H-1,2,3-triazole-5-carboxylic acid Catalog No.:AA01BA86 CAS No.:103264-49-9 MDL No.:MFCD11557215 MF:C10H9N3O2 MW:203.1974
7-benzyl-2-(4-fluorophenyl)-3H,4H,5H,6H,7H,8H-pyrido[3,4-d]pyrimidin-4-one Catalog No.:AA01BE9X CAS No.:1031970-76-9 MDL No.:MFCD14729816 MF:C20H18FN3O MW:335.3748	methyl 3-(4-cyanophenyl)prop-2-ynoate Catalog No.:AA01BFXC CAS No.:1032041-58-9 MDL No.:MFCD13191992 MF:C11H7NO2 MW:185.1788
8-Methyl-2-indolizinecarboxylic acid Catalog No.:AA01BKB1 CAS No.:103261-63-8 MDL No.:MFCD05157591 MF:C10H9NO2 MW:175.184	4'-Fluoro-3'-(trifluoromethyl)-[1,1'-biphenyl]-4-carbaldehyde Catalog No.:AA01BPGS CAS No.:1032506-87-8 MDL No.:MFCD08457041 MF:C14H8F4O MW:268.2063
(4-methyl-1,2-oxazol-3-yl)methanol Catalog No.:AA01BUUH CAS No.:103245-31-4 MDL No.:MFCD22571686 MF:C5H7NO2 MW:113.1146	Methyl 3-{[(tert-butoxy)carbonyl]amino}pentanoate Catalog No.:AA01BVQN CAS No.:1032506-51-6 MDL No.:MFCD08457624 MF:C11H21NO4 MW:231.2887
5-(chloromethyl)-3,4-dihydro-1H-2-benzopyran Catalog No.:AA01BZYI CAS No.:1032590-02-5 MDL No.:MFCD20637534 MF:C10H11ClO MW:182.6467	decahydroazulen-2-one Catalog No.:AA01DX4O CAS No.:103274-00-6 MDL No.:MFCD24692496 MF:C10H16O MW:152.2334
Vapreotide Catalog No.:AA01DZBK CAS No.:103222-11-3 MDL No.:MFCD30489723 MF:C57H70N12O9S2 MW:1131.3707	3-amino-1H-pyrazole-5-carboxylic acid hydrochloride Catalog No.:AA01F26W CAS No.:1032334-56-7 MDL No.:MFCD09431136 MF:C4H6ClN3O2 MW:163.5623
Methyl 4-(3-nitrophenyl)-3-oxobutanoate Catalog No.:AA01F303 CAS No.:1032507-14-4 MDL No.:MFCD08457138 MF:C11H11NO5 MW:237.2087	Methyl 4-(3,4-difluorophenyl)-3-oxobutanoate Catalog No.:AA01F7JT CAS No.:1032506-99-2 MDL No.:MFCD08457118 MF:C11H10F2O3 MW:228.1921
2'-Methoxy-5'-methyl-3'-nitroacetophenone Catalog No.:AA01FBDG CAS No.:103204-71-3 MDL No.:MFCD03789147 MF:C10H11NO4 MW:209.1986	2-Bromo-4,6-dichlorobenzenesulfonamide Catalog No.:AA01FCFK CAS No.:1032507-43-9 MDL No.:MFCD09800659 MF:C6H4BrCl2NO2S MW:304.9765
4-Methyl-1-propylpiperidine Catalog No.:AA01FF9O CAS No.:103199-82-2 MDL No.:MFCD00089156 MF:C9H19N MW:141.2539	3-methylbutyl 2-(3-oxopiperazin-2-yl)acetate Catalog No.:AA01FO7H CAS No.:1032338-42-3 MDL No.:MFCD08700370 MF:C11H20N2O3 MW:228.2881
Dimethyl 2-[(3-{[3-methoxy-1-(methoxycarbonyl)-3-oxopropyl]amino}propyl)amino]succinate Catalog No.:AA01FO8K CAS No.:1032338-61-6 MDL No.: MF:C15H26N2O8 MW:362.3755	4(1H)-Pyridinone, 2,6-dimethyl-1-phenyl-, hydrochloride Catalog No.:AA01FOPD CAS No.:103206-23-1 MDL No.:MFCD00035336 MF:C13H14ClNO MW:235.7094
3-[4-Fluoro-3-(trifluoromethyl)phenyl]benzonitrile Catalog No.:AA0093YG CAS No.:1032506-84-5 MDL No.:MFCD08457045 MF:C14H7F4N MW:265.2057	2-(4-Bromo-3-hydroxy-2-quinolinyl)-1H-indene-1,3(2H)-dione Catalog No.:AA01DNP7 CAS No.:10319-14-9 MDL No.:MFCD00071862 MF:C18H10BrNO3 MW:368.1809
Tetramethylcis,trans,cis-1,2,3,4-Cyclobutanetetracarboxylate Catalog No.:AA01FPQE CAS No.:1032-95-7 MDL No.:MFCD00013269 MF:C12H16O8 MW:288.2506	1-(4-Ethoxyphenyl)-1-propanol Catalog No.:AA0090NS CAS No.:1031927-88-4 MDL No.:MFCD09991469 MF:C11H16O2 MW:180.2435