Fine-Tuning the Nucleophilic Reactivities of Boron Ate Complexes Derived from Aryl and Heteroaryl Boronic Esters

Guillaume Berionni, Artem I. Leonov, Peter Mayer, Armin R. Ofial, and Herbert Mayr*
Dedicated to Dr. Klaus Rçmer on the occasion of his 75th birthday

Boron ate complexes (BACs), which are readily available by treatment of boronic esters R-B(OR)2 with organolithium compounds, are air-stable, functional-group-tolerant nucleophiles,[1] which undergo various noncatalyzed reactions with electrophiles.[2–5] Their treatment with trifluoroacetic anhydride yields intermediate borinic esters which undergo stereoselective allylation reactions with aldehydes, ketones, and imines, when allylboronates are used as precursors.[2]

Following the principle of the Zweifel olefination[3] (Scheme 1, reaction 1), Aggarwal et al. recently reported that treatment of BACs with suitable electrophiles led to the stereospecific coupling of arenes with secondary alkyl groups (Scheme 1, reaction 2).[4]

In contrast, BACs with less-electron-rich arenes (Scheme 1, reaction 3) were attacked by electrophiles at the boron-substituted sp3-hybridized carbon, and the coupling products R-E were formed with a high degree of inversion.[5] Chiral BACs, derived from secondary boronic esters, reacted in this way with a broad range of carbon-, oxygen- and nitrogen-centered electrophiles, including carbenium and iminium ions.[5]

Borate salts M+ arylBX3 with electron-rich arene rings, on the other hand, are known to react with electrophiles at the ipso position of the aryl ring.[6] We have recently demonstrated that the nucleophilicities of thiophenes, furans, and indoles bearing boron substituents, such as -B(OR)3, -BF3,-B(pin), and -B(MIDA) (MIDA = N-methyliminodiacetate), span a reactivity range of ten orders of magnitude.[7] We now report that BACs with two aryl rings behave similarly and describe their isolation and X-ray structures as well as the determination of their nucleophilicities by the benzhydrylium
methodology.[8]

Following a procedure by Brown,[1a,b] we added the thienyl boronic esters 1 a–d to ethereal solutions of the trifluoromethylated aryllithium compounds 2 and 2’ and then removed the solvent by evaporation to produce the lithium BACs (3–4)-Li+ as colorless crystalline solids (Scheme 2). The 11B NMR spectra of all BACs show a sharp resonance at d+ 2 to + 10 ppm that is characteristic of an anionic tetracoordinated boron atom derived from boronic esters.[1] No decomposition of these BACs in CD3CN solutions was observed by 1 H NMR spectroscopy over several days at 208C.[9]

As shown in Scheme 3, addition of thienyl- and furyllithium derivatives 5 and 5’ to the pinacol boronates 6 and 7 produced the respective BACs (8–14)-Li+ in good yields. The tetraethylammonium salt 8 Et4N+ was obtained by cation metathesis from 8-Li+ with Et4N+Cl.

Crystals of 3 a-Li+·(MeCN)3 suitable for X-ray analysis were grown by storing a concentrated MeCN solution of 3 aLi+ at 0 8C for one week. Its solid-state structure (Figure 1 a) shows that the lithium cation is coordinated to one oxygen of the pinacol moiety (Li–O1 = 1.924 ) as well as to three MeCN molecules (Li–N = 2.070 average).[10] Single crystals of the catechol borate 4 d-Li+·(THF)3 were obtained by vapor diffusion of n-pentane into its solution in THF. Figure 1 b shows that Li+ is coordinated to a catechol oxygen and to three THF molecules.[10] The quaternary boron atoms in both BACs have perfect tetrahedral environments (tetrahedral character > 99.9%).[11, 12]

The kinetics of the reactions of the BACs 3–4 and 8–14 with the benzhydrylium ions 15 a–d were monitored by timeresolved UV/Vis spectroscopy in CH3CN at the lmax of 15 (Table 1). In the presence of more than ten equivalents of the BACs, monoexponential decays of the benzhydrylium ions absorbances were observed, indicating pseudo-first-order kinetics. The second-order rate constants k2 reported in Table 2 were derived from the slopes of the plots of kobs (s1) versus the concentration of the BACs (see the Supporting Information).

Kinetic experiments revealed that 8-Li+ was three times less reactive than its sodium analogue 8-Na+ (Scheme 4),[13] in line with the coordination of the Li+ cation to an oxygen atom of the pinacol ligand, which decreases the electron density of the thiophene–boron bond. The reactivity of 8-Et4N+ is in between that of 8-Na+ and 8-Li+, indicating that Et4N+ slightly reduces the nucleophilicity of 8, probably by the formation of a CH···O hydrogen bond with the oxygen atoms of the pinacol ligand.[14] Nevertheless, the kinetic data show that counterions have only a small effect on the nucleophilicities of BACs in CH3CN.

The small values of the Hammett reaction constants (1 1), derived from the correlations in Figure 2, indicate a transition state resembling a s-adduct (Scheme 5), in which the cleavage of the CB bond is not far advanced. As shown in Scheme 6, the reaction of the NMe2 derivative 12-Li+ with electrophiles is not regioselective, and the attack at the thiophene ring of 12-Li+ is only slightly faster than the attack at the dimethylaniline ring. As electrophilic attack at the aryl group is least likely when these are carrying electron-withdrawing groups, the aryl lithium compounds 2 and 2’ are often used for the activation of boronic esters in synthetic applications.[4, 5]

Scheme 7 shows that the ethylene glycol and neopentyl glycol derived BACs 3 b, 3 c, and 4 c are roughly 104 times more reactive than the pinacol and catechol BACs 3 a, 4 a, and 4 d, in line with previous qualitative observations.[15] The origin of these differences is revealed by quantum chemical calculations. It has already been reported that catechol boronates are significantly stronger Lewis acids than ethylene glycol and neopentyl glycol derived boronates because a phenolate oxgen exerts a weaker +M effect than an alkoxide oxygen.[16]

In line with these findings we calculated that the protodeborylation of a catechol-derived BAC is significantly less exothermic than than the analogous reaction of the other BACs (Scheme 8). The fact that the nucleophilicity of the catechol-derived BAC 4 d is 104 times lower than that of 4 c (Scheme 7) shows that a fraction of this difference in reaction energies is already observed in the transition states of the
reactions with benzydrylium ions.

On the other hand, similar exothermicities are calculated for the proto-deborylations of the B(pin), B(gly), and B(neo) derivatives (Scheme 8). For that reason, we can conclude that the difference in nucleophilicities of the BACs 3 a and 3 b is exclusively due to steric effects. The identical nucleophilicities of 3 b and 3 c, in line with the comparable reaction energies of the corresponding proto-deborylations shown in Scheme 8, furthermore show that conceivable stereoelectronic effects (ideal overlap of the empty p orbital at boron with the oxygen lone pair) do not increase the reactivity of the neopentyl derivatives 3 c and 4 c.

Substitution of the second-order rate constants k2 determined in this work into Equation (1),[7, 8] which characterizes electrophiles by the electrophilicity parameter E and nuclelg k2 ð20 CÞ ¼ sNðN þ EÞ ð1Þ ophiles by the nucleophilicity parameter N and the sensitivity parameter sN, allows us to determine N and sN for the BACs 3–4 and 8–14 (Table 2) and to compare them with related nucleophiles (Figure 3). 

In conclusion, we have found that the nucleophilic reactivity of the furylboronate 1’ (N = 2.90) is increased by a factor > 105 by the addition of 4-CF3-phenyllithium (2’) to give 14 (Figure 3). A somewhat stronger activation can be achieved with aryllithium compounds carrying electrondonating substituents, but one has to take care that in these cases electrophiles are not directed to the aryl ring (Scheme 6).

While the nucleophilic reactivies of the BACs depend only slightly on their counterions, the nature of the diol ligand has a profound effect on its nucleophilicity. Thus, the -B(gly) and-B(neo) derivatives are 104 times more reactive than the-B(pin) and -B(cat) derivatives. With these data in hand, we now have a quantitative basis for fine-tuning the nucleophilic reactivities of boron ate complexes for synthetic applications.

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2,5-Dioxo-3-sulfo-1-pyrrolidinyl 6-[(4-azido-2-nitrophenyl)amino]hexanoate Catalog No.:AA0007NE CAS No.:102568-43-4 MDL No.:MFCD00054986 MF:C16H18N6O9S MW:470.4139	Ethyl 2-bromobenzoate-6-boronic acid pinacol ester Catalog No.:AA0007ON CAS No.:1025708-01-3 MDL No.:MFCD08669582 MF:C15H20BBrO4 MW:355.0319
5-Bromo-4-isopropylthiazol-2-amine Catalog No.:AA0007O1 CAS No.:1025700-49-5 MDL No.:MFCD09834790 MF:C6H9BrN2S MW:221.1181	Tert-butyl 3-formyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-1H-indole-1-carboxylate Catalog No.:AA0007O0 CAS No.:1025707-92-9 MDL No.:MFCD07364063 MF:C20H26BNO5 MW:371.2351
2-(3,4-Difluoro-2-methylphenyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Catalog No.:AA0007NY CAS No.:1025707-97-4 MDL No.:MFCD08669570 MF:C13H17BF2O2 MW:254.0807	(8-Methoxyquinolin-5-yl)boronic acid Catalog No.:AA0007PA CAS No.:1025735-47-0 MDL No.:MFCD07357508 MF:C10H10BNO3 MW:203.0023
(3R,4S,5R,6R)-6-(Hydroxymethyl)tetrahydro-2H-pyran-2,3,4,5-tetraol Catalog No.:AA0007OI CAS No.:10257-28-0 MDL No.:MFCD00151230 MF:C6H12O6 MW:180.1559	1-(3-Chlorophenyl)piperidine Catalog No.:AA0007NP CAS No.:102563-84-8 MDL No.:MFCD10699658 MF:C11H14ClN MW:195.6886
5-Bromo-4-isopropylthiazole Catalog No.:AA0007O2 CAS No.:1025700-46-2 MDL No.:MFCD18070981 MF:C6H8BrNS MW:206.1034	Methyl 3-bromo-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate Catalog No.:AA0007OK CAS No.:1025718-78-8 MDL No.:MFCD12405334 MF:C14H18BBrO4 MW:341.0053
3,4-Dihydro-6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2H-pyran Catalog No.:AA0007NZ CAS No.:1025707-93-0 MDL No.:MFCD07368233 MF:C11H19BO3 MW:210.0778	(3',4'-Dichloro-[1,1'-biphenyl]-4-yl)boronic acid Catalog No.:AA0007P9 CAS No.:1025736-43-9 MDL No.:MFCD08544390 MF:C12H9BCl2O2 MW:266.9157
3-(3,5-Dimethyl-1H-pyrazol-1-yl)phenylboronic acid Catalog No.:AA0007PB CAS No.:1025735-46-9 MDL No.:MFCD08572151 MF:C11H13BN2O2 MW:216.0441	5-(4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)pyrimidine-2-carbonitrile Catalog No.:AA0007OM CAS No.:1025708-31-9 MDL No.:MFCD08669562 MF:C11H14BN3O2 MW:231.0588
BMS-777607 Catalog No.:AA0007PD CAS No.:1025720-94-8 MDL No.:MFCD16495773 MF:C25H19ClF2N4O4 MW:512.8926	1-Methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-3-(trifluoromethyl)-1H-pyrazole Catalog No.:AA0007PF CAS No.:1025719-23-6 MDL No.:MFCD12828677 MF:C11H16BF3N2O2 MW:276.0631
2-(4-Bromofuran-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane Catalog No.:AA0007PJ CAS No.:1025719-11-2 MDL No.:MFCD12405449 MF:C10H14BBrO3 MW:272.9314	3-Bromo-5-(trifluoromethyl)phenol Catalog No.:AA0007PT CAS No.:1025718-84-6 MDL No.:MFCD11041083 MF:C7H4BrF3O MW:241.0053
1-BOC-5-bromopyrrolo[2,3-b]pyridine-3-boronic acid, pinacol ester Catalog No.:AA0007PI CAS No.:1025719-14-5 MDL No.:MFCD12407269 MF:C18H24BBrN2O4 MW:423.1092	3-(Cyclopropylmethyl)thiophenylboronic acid Catalog No.:AA0007Q0 CAS No.:1025746-82-0 MDL No.:MFCD09025757 MF:C10H13BO2S MW:208.0850
Methyl 5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)nicotinate Catalog No.:AA0007PQ CAS No.:1025718-91-5 MDL No.:MFCD09027079 MF:C13H18BNO4 MW:263.0973	(S)-Di-tert-butyl 2-(3-((S)-6-amino-1-(tert-butoxy)-1-oxohexan-2-yl)ureido)pentanedioate Catalog No.:AA0007PY CAS No.:1025796-31-9 MDL No.:MFCD28898592 MF:C24H45N3O7 MW:487.6300
2-Fluoro-6-(tributylstannyl)pyridine Catalog No.:AA0007Q4 CAS No.:1025744-38-0 MDL No.:MFCD09025793 MF:C17H30FNSn MW:386.1262	2-Methoxy-5-(tributylstannyl)thiazole Catalog No.:AA0007Q3 CAS No.:1025744-42-6 MDL No.:MFCD09025806 MF:C16H31NOSSn MW:404.1894
Benzyl 3-oxoazepane-1-carboxylate Catalog No.:AA0007QN CAS No.:1025828-21-0 MDL No.:MFCD19687798 MF:C14H17NO3 MW:247.2897	4-(3,5-Dichlorophenyl)benzonitrile Catalog No.:AA0007S1 CAS No.:1025992-48-6 MDL No.:MFCD20529470 MF:C13H7Cl2N MW:248.1074
2,7-dibromo-Pyrene Catalog No.:AA0007SI CAS No.:102587-98-4 MDL No.:MFCD09909862 MF:C16H8Br2 MW:360.0427	(4-Chlorothiazol-5-yl)methanol Catalog No.:AA0007S4 CAS No.:1025936-09-7 MDL No.:MFCD24848905 MF:C4H4ClNOS MW:149.5987
2-((4-(Trifluoromethyl)phenyl)thio)acetic acid Catalog No.:AA0007R3 CAS No.:102582-93-4 MDL No.:MFCD00236351 MF:C9H7F3O2S MW:236.2109	(S)-2-(2-(Benzofuran-6-carbonyl)-5,7-dichloro-1,2,3,4-tetrahydroisoquinoline-6-carboxamido)-3-(3-(methylsulfonyl)phenyl)propanoic acid Catalog No.:AA0007S2 CAS No.:1025967-78-5 MDL No.:MFCD28502439 MF:C29H24Cl2N2O7S MW:615.4811
Bicyclo[2.2.2]octa-2,5-diene-2-carboxylicacid Catalog No.:AA0007SE CAS No.:102589-30-0 MDL No.:MFCD16251231 MF:C9H10O2 MW:150.1745	Z-Gly-Gly-Arg-AMC HCl Catalog No.:AA0007SV CAS No.:102601-58-1 MDL No.:MFCD00039016 MF:C9H10ClNO3 MW:215.6336
2-(4-bromo-2-methoxyphenyl)acetic acid Catalog No.:AA0007TF CAS No.:1026089-09-7 MDL No.:MFCD11847505 MF:C9H9BrO3 MW:245.0700	CAPSO Sodium Salt Catalog No.:AA0007SY CAS No.:102601-34-3 MDL No.:MFCD00070063 MF:C9H18NNaO4S MW:259.2983
1-Tosyl-1H-pyrrole-2-carbaldehyde Catalog No.:AA0007UU CAS No.:102619-05-6 MDL No.:MFCD00671580 MF:C12H11NO3S MW:249.2856	Tetrabenazine (+)- Catalog No.:AA0007ST CAS No.:1026016-83-0 MDL No.:MFCD08461052 MF:C19H27NO3 MW:317.4226
2-Methyl-N-phenyl-1,2,3,4-tetrahydroquinolin-4-amine Catalog No.:AA0007TD CAS No.:1026-05-7 MDL No.:MFCD00183927 MF:C16H18N2 MW:238.3275	Diallyl terephthalate Catalog No.:AA0007T2 CAS No.:1026-92-2 MDL No.:MFCD00080462 MF:C14H14O4 MW:246.2586
(S)-2-Amino-2-(m-tolyl)ethanol Catalog No.:AA0007VJ CAS No.:1026230-99-8 MDL No.:MFCD09253708 MF:C9H13NO MW:151.2056	Benzoic acid, 3-methoxy-, ethyl ester Catalog No.:AA0007SN CAS No.:10259-22-0 MDL No.:MFCD00015149 MF:C10H12O3 MW:180.2005
2-Pyridinecarboxaldehyde, 3-nitro- Catalog No.:AA0007TZ CAS No.:10261-94-6 MDL No.:MFCD10696871 MF:C6H4N2O3 MW:152.1076	1,5-Naphthyridin-2(1H)-one Catalog No.:AA0007U1 CAS No.:10261-82-2 MDL No.:MFCD11877925 MF:C8H6N2O MW:146.1460
2-Bromoacetyl-6-methoxynaphtalene Catalog No.:AA0007VH CAS No.:10262-65-4 MDL No.:MFCD03964189 MF:C13H11BrO2 MW:279.1292	8-bromo-2-(chloromethyl)imidazo[1,2-a]pyridine hydrochloride Catalog No.:AA0007VK CAS No.:1026212-65-6 MDL No.:MFCD11976182 MF:C8H7BrCl2N2 MW:281.9646
5-Bromoimidazo[1,2-a]pyridine-2-carboxylic Acid Catalog No.:AA0007VM CAS No.:1026201-52-4 MDL No.:MFCD11043994 MF:C8H5BrN2O2 MW:241.0415	Azetidine-3-carboxylic acid hydrochloride Catalog No.:AA0007VX CAS No.:102624-96-4 MDL No.:MFCD06796562 MF:C4H8ClNO2 MW:137.5648
8-Bromoimidazo[1,2-a]pyridine-2-carboxylic acid Catalog No.:AA0007VN CAS No.:1026201-45-5 MDL No.:MFCD12195903 MF:C8H5BrN2O2 MW:241.0415	β-D-Glucopyranuronic acid, 1-[2-[(2,3-dimethylphenyl)amino]benzoate] Catalog No.:AA0007W1 CAS No.:102623-18-7 MDL No.:MFCD09840854 MF:C21H23NO8 MW:417.4092
Protoporphyrin IX cobalt chloride Catalog No.:AA008RK4 CAS No.:102601-60-5 MDL No.:MFCD00216774 MF:C34H32ClCoN4O4 MW:655.0285	2H-Pyrido[3,2-b]-1,4-oxazin-3(4H)-one, 6-[[5-fluoro-2-[(3,4,5-trimethoxyphenyl)amino]-4-pyrimidinyl]amino]-2,2-dimethyl-4-[(phosphonooxy)methyl]-, sodium salt (1:2) Catalog No.:AA008SQH CAS No.:1025687-58-4 MDL No.:MFCD15146370 MF:C23H24FN6Na2O9P MW:624.4232
Decanoic Acid-d3 Catalog No.:AA008SW2 CAS No.:102611-15-4 MDL No.:MFCD00144050 MF:C10H17D3O2 MW:175.2831	3-METHYL-D3-PYRIDINE Catalog No.:AA008SXH CAS No.:10259-17-3 MDL No.:MFCD00144911 MF:C6H4D3N MW:96.1450
5-(2-Fluorophenyl)thiazol-2-amine Catalog No.:AA008SZY CAS No.:1025927-65-4 MDL No.:MFCD11846733 MF:C9H7FN2S MW:194.2287	8-bromo-6-methylimidazo[1,2-a]pyrazine Catalog No.:AA008UPM CAS No.:1025976-69-5 MDL No.:MFCD12033240 MF:C7H6BrN3 MW:212.0466
Potassium (e)-3-methoxyprop-1-enyltrifluoroborate Catalog No.:AA008WO3 CAS No.:1025825-38-0 MDL No.:MFCD09750463 MF:C4H7BF3KO MW:178.0023	NSC12 Catalog No.:AA008ZRY CAS No.:102586-30-1 MDL No.:MFCD31544308 MF:C24H34F6O3 MW:484.5154
(4-((diisopropylamino)methyl)phenyl)boronic acid Catalog No.:AA0095F2 CAS No.:1025900-35-9 MDL No.:MFCD28384212 MF:C13H22BNO2 MW:235.1303	Inhibitor 6e (PRMT1 inhibitor 6e) Catalog No.:AA0097CS CAS No.:1025948-98-4 MDL No.: MF:C20H7Br6NO5 MW:820.6973
Pentyl 2-(3-oxo-2-piperazinyl)acetate Catalog No.:AA009A1M CAS No.:1025736-40-6 MDL No.:MFCD08081802 MF:C11H20N2O3 MW:228.2881	Decyl 3-oxo-2-piperazineacetate Catalog No.:AA009N5A CAS No.:1025736-41-7 MDL No.:MFCD08096774 MF:C16H30N2O3 MW:298.4210
[4-(Trifluoromethoxy)phenyl]methyl acetate Catalog No.:AA00H9QV CAS No.:102606-99-5 MDL No.:MFCD30834415 MF:C10H9F3O3 MW:234.1719	2-Amino-4-(benzyloxy)phenol Catalog No.:AA00H9QQ CAS No.:102580-07-4 MDL No.:MFCD24646652 MF:C13H13NO2 MW:215.2478
1-(4-{4-[5-(2-furyl)-1H-pyrazol-3-yl]piperidino}-3-nitrophenyl)-1-ethanone Catalog No.:AA00IN8Y CAS No.:1025725-16-9 MDL No.:MFCD05974876 MF:C20H20N4O4 MW:380.3972	N-[3-(dimethylamino)propyl]-4-nitro-2-(trifluoromethyl)benzenaminium chloride Catalog No.:AA00INH9 CAS No.:1025759-04-9 MDL No.:MFCD04035620 MF:C12H17ClF3N3O2 MW:327.7305
Ethyl 5-(3-nitrophenyl)-1H-pyrazole-3-carboxylate Catalog No.:AA00IQYR CAS No.:1025724-57-5 MDL No.:MFCD00245769 MF:C12H11N3O4 MW:261.2334	methyl 2-({[1-methyl-3-(trifluoromethyl)-1H-pyrazol-4-yl]carbonyl}amino)butanoate Catalog No.:AA00IR40 CAS No.:1026104-65-3 MDL No.:MFCD03305850 MF:C11H14F3N3O3 MW:293.2424
1,1,1-trifluoro-3-{4-[5-(4-methoxyphenyl)-1H-pyrazol-3-yl]piperidino}-2-propanol Catalog No.:AA00IRGT CAS No.:1025769-00-9 MDL No.:MFCD05668943 MF:C18H22F3N3O2 MW:369.3814	5-(3-Amino-phenyl)-1H-pyrazole-3-carboxylicacidethylester Catalog No.:AA00IRXL CAS No.:1025724-78-0 MDL No.:MFCD03848687 MF:C12H13N3O2 MW:231.2505
4-chloro-6-{4-[5-(2-thienyl)-1H-pyrazol-3-yl]piperidino}-2-pyrimidinylamine Catalog No.:AA00ISFS CAS No.:1025762-04-2 MDL No.:MFCD05256350 MF:C16H17ClN6S MW:360.8644	ethyl (2E)-3-[(2-chloro-6-methylphenyl)amino]-2-cyanoprop-2-enoate Catalog No.:AA00ITBT CAS No.:1026046-70-7 MDL No.:MFCD00245418 MF:C13H13ClN2O2 MW:264.7075
(2Z)-2-{[4-(dimethylamino)phenyl]methylidene}-5,6-dimethoxy-2,3-dihydro-1H-inden-1-one Catalog No.:AA00ITCQ CAS No.:1025637-00-6 MDL No.:MFCD01567350 MF:C20H21NO3 MW:323.3856	(2Z)-3-(4-hydroxyphenyl)-2-(2-methylpropane-2-sulfonyl)prop-2-enenitrile Catalog No.:AA00ITDD CAS No.:1025704-84-0 MDL No.:MFCD01897603 MF:C13H15NO3S MW:265.3281
6,14,14-trimethyl-10-[(E)-2-phenylethenyl]-2,9-diazatricyclo[9.4.0.0^{3,8}]pentadeca-1(11),3(8),4,6-tetraen-12-one Catalog No.:AA00ITDF CAS No.:1025658-27-8 MDL No.:MFCD00246067 MF:C24H26N2O MW:358.4760	(2Z)-3-[(3-acetylphenyl)amino]-2-(4-methylbenzenesulfonyl)prop-2-enenitrile Catalog No.:AA00ITEG CAS No.:1025668-88-5 MDL No.:MFCD01567392 MF:C18H16N2O3S MW:340.3962
N'-[(1E)-(5,7-dimethyl-4-oxo-4H-chromen-3-yl)methylidene]-4-methylbenzene-1-sulfonohydrazide Catalog No.:AA00ITEQ CAS No.:1026230-71-6 MDL No.:MFCD01567451 MF:C19H18N2O4S MW:370.4222	12-acetyl-1,4-dioxa-9-thia-12-azadispiro[4.2.4.2]tetradecane-11-carboxylic acid Catalog No.:AA00IUFG CAS No.:1025707-45-2 MDL No.:MFCD08281866 MF:C13H19NO5S MW:301.3587
6,8-dichloro-2-[(E)-2-(4-chloro-3-nitrophenyl)ethenyl]-4H-3,1-benzoxazin-4-one Catalog No.:AA00IV42 CAS No.:1025679-04-2 MDL No.:MFCD00170881 MF:C16H7Cl3N2O4 MW:397.5968	ethyl (2Z)-2-cyano-3-{[(4-fluorophenyl)methyl]amino}prop-2-enoate Catalog No.:AA00IV6P CAS No.:1025644-67-0 MDL No.:MFCD01567352 MF:C13H13FN2O2 MW:248.2529
(2E)-2-{[(3,4-dimethoxyphenyl)amino]methylidene}-3-oxo-N-phenylbutanamide Catalog No.:AA00IV75 CAS No.:1025630-40-3 MDL No.:MFCD00955262 MF:C19H20N2O4 MW:340.3731	[(E)-[(4-{[3-chloro-5-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)methylidene]amino]urea Catalog No.:AA00IV7R CAS No.:1025634-84-7 MDL No.:MFCD00955427 MF:C14H10ClF3N4O2 MW:358.7030
4-chloro-6-{4-[5-(2-furyl)-1H-pyrazol-3-yl]piperidino}-2-pyrimidinylamine Catalog No.:AA00IW2T CAS No.:1026080-38-5 MDL No.:MFCD05974964 MF:C16H17ClN6O MW:344.7988	3-chloro-N-[3-(dimethylamino)propyl]-1,4-dioxo-1,4-dihydro-2-naphthalenaminium chloride Catalog No.:AA00IW8Y CAS No.:1025759-03-8 MDL No.:MFCD03617577 MF:C15H18Cl2N2O2 MW:329.2216
4-(4-ethoxyphenyl)-2-{[2-(1H-indol-3-yl)ethyl]amino}-4-oxobutanoic acid Catalog No.:AA00IWRA CAS No.:1025773-67-4 MDL No.:MFCD00955003 MF:C22H24N2O4 MW:380.437	(2E)-2-({[4-fluoro-2-(trifluoromethyl)phenyl]amino}methylidene)-4,4-dimethyl-3-oxopentanenitrile Catalog No.:AA00IX7K CAS No.:1025659-82-8 MDL No.:MFCD00245423 MF:C15H14F4N2O MW:314.2781
2-{[(2H-1,3-benzodioxol-5-yl)amino]methylidene}propanedinitrile Catalog No.:AA00IX8K CAS No.:1025997-07-2 MDL No.:MFCD00246013 MF:C11H7N3O2 MW:213.1922	N-(5-methyl-1,2-oxazol-3-yl)-2-(trifluoromethyl)benzene-1-sulfonamide Catalog No.:AA00IX8T CAS No.:1025797-90-3 MDL No.:MFCD00955225 MF:C11H9F3N2O3S MW:306.261
ethyl 4,4,4-trifluoro-3-hydroxy-2-(methoxyimino)butanoate Catalog No.:AA00IXZ4 CAS No.:102608-31-1 MDL No.:MFCD03012126 MF:C7H10F3NO4 MW:229.1538	2-(4-{5-[3-(trifluoromethyl)phenyl]-1H-pyrazol-3-yl}piperidino)acetonitrile Catalog No.:AA00IYK4 CAS No.:1025724-64-4 MDL No.:MFCD05256161 MF:C17H17F3N4 MW:334.3389
4-chloro-6-{4-[5-(4-methoxyphenyl)-1H-pyrazol-3-yl]piperidino}-2-pyrimidinamine Catalog No.:AA00IZ48 CAS No.:1026093-00-4 MDL No.:MFCD05668930 MF:C19H21ClN6O MW:384.8626	(2Z)-3-[(4-chloro-6-methylpyrimidin-2-yl)amino]-2-(4-methylbenzenesulfonyl)prop-2-enenitrile Catalog No.:AA00IZZY CAS No.:1025678-47-0 MDL No.:MFCD00245823 MF:C15H13ClN4O2S MW:348.8073
(3Z)-3-(4-chlorobenzenesulfonyl)-4-[(4-fluorophenyl)amino]but-3-en-2-one Catalog No.:AA00J00L CAS No.:1025680-73-2 MDL No.:MFCD00246096 MF:C16H13ClFNO3S MW:353.7957	(2Z)-2-{[4-(difluoromethoxy)phenyl]methylidene}-5,6-dimethoxy-2,3-dihydro-1H-inden-1-one Catalog No.:AA00J01F CAS No.:1025637-49-3 MDL No.:MFCD01567456 MF:C19H16F2O4 MW:346.3247
3-(1H-imidazol-1-ylcarbonyl)-1H-indazole Catalog No.:AA00J0M7 CAS No.:1025910-84-2 MDL No.:MFCD26130293 MF:C11H8N4O MW:212.2074	Methyl-(5-methyl-1H-pyrazol-3-ylmethyl)amine hydrochloride Catalog No.:AA00J0VH CAS No.:1025735-75-4 MDL No.:MFCD14707634 MF:C6H12ClN3 MW:161.6326
N-(3-chlorophenyl)-2-(propylamino)propanamide hydrochloride Catalog No.:AA019IP3 CAS No.:1025735-37-8 MDL No.:MFCD07308453 MF:C12H18Cl2N2O MW:277.1901	{[2,5-dimethyl-1-(4-methylphenyl)-1H-pyrrol-3-yl]methyl}trimethylazanium iodide Catalog No.:AA019OGZ CAS No.:1025737-67-0 MDL No.:MFCD07339030 MF:C17H25IN2 MW:384.2983
5-(Chlorosulfonyl)-4-fluoro-2-methylbenzoic acid Catalog No.:AA01A1IN CAS No.:1026030-54-5 MDL No.:MFCD03120462 MF:C8H6ClFO4S MW:252.6472	2-Azido-N-phenylacetamide Catalog No.:AA01A1U1 CAS No.:10258-71-6 MDL No.:MFCD14652253 MF:C8H8N4O MW:176.1753
4-methoxypyridazin-3-amine Catalog No.:AA01A5PS CAS No.:1026194-47-7 MDL No.:MFCD19213749 MF:C5H7N3O MW:125.1286	2-amino-N-ethyl-5-fluorobenzene-1-sulfonamide Catalog No.:AA01A5YV CAS No.:1026183-64-1 MDL No.:MFCD12774449 MF:C8H11FN2O2S MW:218.2485
(1-(4-Aminophenyl)-1H-1,2,3-triazol-4-yl)methanol Catalog No.:AA01A6PY CAS No.:1026133-62-9 MDL No.:MFCD11844966 MF:C9H10N4O MW:190.2019	(1S)-1-(4-Bromo-2-fluorophenyl)ethan-1-ol Catalog No.:AA01BBJC CAS No.:1026088-11-8 MDL No.:MFCD22570034 MF:C8H8BrFO MW:219.0509
1-(carboxymethyl)-6-oxo-1,6-dihydropyridine-3-carboxylic acid Catalog No.:AA01BCV8 CAS No.:1025871-64-0 MDL No.:MFCD19691373 MF:C8H7NO5 MW:197.1449	N-{1-azabicyclo[3.2.1]octan-4-ylidene}hydroxylamine Catalog No.:AA01BG86 CAS No.:1026035-03-9 MDL No.:MFCD28125072 MF:C7H12N2O MW:140.1830
1,2-difluoro-4-[(E)-2-nitroethenyl]benzene Catalog No.:AA01DX4I CAS No.:1025692-47-0 MDL No.:MFCD01317618 MF:C8H5F2NO2 MW:185.1276	(S, Z)-4-((1-(tert-butylamino)-3-((4-morpholino-1, 2, 5- thiadiazol-3-yl)oxy)propan-2-yl)oxy)-4-oxobut-2-enoic acid Catalog No.:AA01EH4M CAS No.:1026075-53-5 MDL No.: MF:C17H26N4O6S MW:414.4765
(5Z)-2-[(2,6-Dichlorophenyl)amino]-5-(6-quinoxalinylmethylene)-4(5H)-thiazolone Catalog No.:AA01ENEK CAS No.:1025821-33-3 MDL No.:MFCD31689261 MF:C18H10Cl2N4OS MW:401.2692	Bis(prop-2-en-1-yl)(pyren-1-ylmethyl)amine Catalog No.:AA01FB25 CAS No.:102592-39-2 MDL No.:MFCD00962124 MF:C23H21N MW:311.4195
Dodecyl 3-oxo-2-piperazineacetate Catalog No.:AA01FO8J CAS No.:1025736-42-8 MDL No.: MF:C18H34N2O3 MW:326.4742	2-Fluoro-5-(Tributylstannyl)Pyridine Catalog No.:AA0007N7 CAS No.:1025687-41-5 MDL No.:MFCD07787406 MF:C17H30FNSn MW:386.1262
Calciumsulfite Catalog No.:AA0007OD CAS No.:10257-55-3 MDL No.:MFCD00040663 MF:CaO3S MW:120.1412	7-amino-6-fluoro-1,2,3,4-tetrahydroisoquinolin-1-one Catalog No.:AA01DX4J CAS No.:1025898-12-7 MDL No.:MFCD20718206 MF:C9H9FN2O MW:180.179
4-(Tributylstannyl)-1H-indole Catalog No.:AA01FFZE CAS No.:1025745-98-5 MDL No.:MFCD09265481 MF:C20H33NSn MW:406.1837	2-Amino-6-(trifluoromethyl)-3-pyridinecarbonitrile Catalog No.:AA0007SQ CAS No.:1026039-34-8 MDL No.:MFCD11106702 MF:C7H4F3N3 MW:187.1220