2019-11-11 11:01:30
AA Blocks offers hard-to-find and hard-to-synthesize products in laboratory quantities as well as bulk quantities like combi-blocks
Charlotte Lorton[a] and Arnaud Voituriez*[a]
1. Introduction
Tricyclic indole backbone is often encountered in natural products and pharmaceuticals. This class of heterocycles, and especially the pyrrolo[1,2-a]indole scaffolds, has attracted much attention due to their potent biological activities (Scheme 1a). As representative examples, mitomycin A and C (compounds 1 and2) are two effective antitumor agents;[1a] the antiparasitic isoborreverine 3[1b–1c] and the antimalarial alkaloid flinderole C(4) [1d–1e] show interesting biological properties and compound 5 acts as sphingosine-1 phosphate (S1P1) antagonist.[1f–1g]
Moreover, compound 6 is a protein kinase C inhibitor selective for isozyme [1h–1i] and isatisine A (7) acts as an anti-HIV agent.[1j] Since the ‘60s, many synthetic pathways have been developed worldwide for the synthesis of the pyrrolo[1,2-a]-indoles, often driven by the interest of the organic chemistry community for the mitomycinoid alkaloids. These strategies have been reviewed in 2016,[2] but in view of the renewed interest of the scientific community for this structure, it seemed to us interesting to make this update. In the context of this mini-review, among the three isomeric structures of the pyrrolo[1,2 a]indoles, our attention will be focused towards the 9H-isomer 8 and its oxidized form, the 9H-pyrrolo[1,2-a]indol-9-one 9, with respect to the 3H- and 1H-isomers (respectively products 10 and 11, Scheme 1b). The articles evoking the syntheses of 9H-pyrrolo[1,2-a]indoles will not be fully detailed in this review.[3] On the other hand, the synthetic methodologies (organometallic or non-metallic) for the synthesis of these three-membered nitrogen-containing rings will be detailed. First, the synthesis of 9H-pyrrolo[1,2-a]indoles will be resumed, and then, in the second part, the preparation of 9Hpyrrolo[1,2-a]indol-9-one derivatives. Before the conclusion, various applications in medicinal chemistry and materials chemistry of these molecules of interest will be summarized.
2. Synthesis of 9H-Pyrrolo[1,2-a]indoles
In this part, the synthetic pathways used for the isolation of
9H-pyrrolo[1,2-a]indole derivatives will be developed. First, the
reactions promoted by non-metallic reagents will be presented.
Both phosphonium and ammonium salts were used, but also acid-promotors, radical precursors, amine-catalyzed and thermal processes. Then will follow metal-catalyzed and metal-promoted reactions, classified according to the type of metal used
(copper, palladium, silver, and others).
2.1. Non-Metal Promoted Reactions
In 1966, Schweizer and Light developed the synthesis of unsubstituted 9H-pyrrolo[1,2-a]indole 8 from indole-2-carboxaldehyde 12 and vinyltriphenylphosphonium bromide, in presence of sodium hydride (Scheme 2a).[4] The product was isolated in 58 % yield. It was noticed in this paper that the structure of this product was first incorrectly assigned to the 3H-pyrrolo-[1,2-a]indole 10.[5] As subsequently demonstrated in numerous examples, it turned out that the initially 3H-isomer formed after the intramolecular Wittig reaction isomerizes in situ to the most stable 9H-isomer.[6] This work is the logical extension of the methodologies used by the same team for the synthesis of 3Hpyrrolizine[5,7] and 2H-chromene derivatives.[8] The same strategy was later successfully applied to the synthesis of polysubstituted 9H-pyrrolo[1,2-a]indole 14,[9] with methoxy- and benzyloxy-substituents in position 7 and 8 (Scheme 2b) or with substituents in positions 6 and 7 (compound 16, Scheme 2c).[10] With substituted-indole-2-carboxaldehydes 17 as starting materials, in presence of methylvinylketone and a benzyltrimethylammonium hydroxide solution, Matsui et al. synthesized five 9Hpyrrolo[1,2a]indoles 18 in moderate yields (Scheme 3a).[11] Inoue described an original reaction of tris(isopropylthio)cyclopropenylium perchlorate 20 with two different indoles 19, in presence of sodium hydride.[12] Two pyrroloindoles 21 were isolated in 51–84 % yield (Scheme 3b).
Starting from 1-keto-1H-pyrrolo[1,2-a]indoles 22, Remers described a new rearrangement, giving direct access to the 9Hpyrrolo[1,2-a]indole structures 23, substituted with a chlorine atom and a methyl 2-oxoacetate group. The two-steps procedure first involves the reaction with oxalyl chloride and then the addition of methanol (Scheme 4).[13] In 2009, Su et al. described the synthesis of twelve (9Hpyrrolo[1,2-a]indole-1,2-diyl)dimethanol analogs 26, using a three-steps methodology (Scheme 5).[14] Reaction of indoline-2-carboxylic acids 24 with different alkoyl- or aroyl chlorides furnished the corresponding protected indolines 25. They were reacted then at 120 °C with dimethyl acetylenedicarboxylate (DMAD) in acetic anhydride. The corresponding pyrroloindoles 26 were isolated in 71–89 % yield, after recrystallization. Some post-functionalizations, included reduction of the diester functions to alcohols and reaction with methyl isocyanate, delivered the desired molecules 27. These products were specifically designed for biological evaluation as antitumor drugs. They are expected to act as DNA bifunctional alkylating agents. They exhibited cytotoxicity against human leukemia and tumor re-mission in nude mice bearing human breast carcinoma MX–1 xenograft. This work and the preliminary interesting biological results highlighted the interest to develop new methodologies for the synthesis of the 9H-pyrrolo[1,2-a]indole backbone (see part 4 for further applications).
Yavari and Esmaeili independently reported a halide and base-free phosphine-promoted Michael addition/intramolecular Wittig reaction (Scheme 6a).[15] Using a stoichiometric quantity of triphenylphosphine, the reaction pathway started with the addition of the phosphine to the dialkylacetylenedicarboxylate 28 (DAAD), to form the zwitterionic species A. This intermediate deprotonates the indole-2-carboxaldehyde 29, which consequently performs a Michael addition on the corresponding vinylphosphonium salt B, to in situ form a phosphorus ylide C. After the intramolecular Wittig reaction, the 3Hpyrrolo[1,2-a]indole derivatives 30 were isolated. In this process, the use of mild reaction conditions (room temperature for 15 minutes) allows isolating the 3H-pyrrolo[1,2-a]indole isomer. In
fact, when the 9-chloro-3H-pyrrolo[1,2-a]indole-2,3-dicarboxylate product was refluxed 24 h in toluene, the authors described the isomerization into the 9H-pyrrolo[1,2-a]indole. As a potential derivatization of these compounds, we can notice that the hydrolysis of 9-chloro-9H-pyrrolo[1,2-a]indole product occurred in a mixture CHCl3/H2O, 24 h at reflux. Even if this synthetic protocol proves to be very efficient in term of conversion rate (96–98 % yield), only three examples using 3-chloro-1H-indole-2-carbaldehydes were showed and at least 1.0 equiv. of triphenylphosphine oxide is formed during the reaction.
Mainly to facilitate the purification issue, we proposed recently to use in this reaction a sub-stoichiometric quantity of trivalent phosphine (Scheme 6b). The in situ chemoselective reduction of the phosphine oxide could be achieved efficiently using 1.0 equiv. of a reducing agent, such as phenylsilane.[16] Even if this catalytic protocol was previously used in different venerable reactions (Wittig, Mitsunobu, Staudinger), that was to the best of our knowledge, the first example of a tandem Michael addition/Wittig reaction, catalytic in phosphine. Using this protocol, it was possible to realize a wide range of Michael addition/intramolecular Wittig reactions, using electron-rich(such as 5-methyl, 5-methoxy and 5-benzyloxy-indoles) and electron-poor substrates (such as 5-fluoro, 5-nitro, and 5 triflateindole-2-carbaldehydes).[17] Using these reaction conditions(60 °C in toluene for 16 h), the most stable 9H-pyrrolo[1,2-a]-indole isomer 31 was directly isolated. In our hand, the use of microwave heating allowed to shorten the reaction time to 2 h, while maintaining excellent yield (93 % yield for the synthesis of the diethyl 7-bromo-9H-pyrrolo[1,2-a]indole-2,3-dicarboxylate product). The structural assignment of this molecule was ascertained by single-crystal X-ray analysis, which verified the formation of the 9H-pyrroloindole isomer.
In our hand, with the 3-chloro-1H-indole-2-carbaldehyde substrate 29, the hydrolysis of the chlorinated intermediate was directly observed (Scheme 7). Subsequent oxidation into the 9H-pyrrolo[1,2-a]indol-9-one derivative 33 was accomplished in 90 % yield, using pyridinium chlorochromate (PCC). The procedure (cyclization/isomerization/hydrolysis/oxidation) could be achieved sequentially in one pot, with 90 % overall yield. In the following, we fully expanded the scope of this catalytic one-pot Michael addition/intramolecular Wittig reaction to the synthesis of numerous nitrogen-containing heterocycles. Notably, pyrrolizine, pyrroloquinoline, dihydroquinoline, and benzothienopyridine backbones were easily obtained using this catalytic protocol.[18]
In the continuity of this study, we introduced alkyl buta-2,3-dienoates as substrate, to open the structural diversity in the 9H-pyrrolo[1,2-a]indole derivatives (Scheme 8a).[19] Different 1H-indole-2-carbaldehydes 34 reacted with allenoates 35, in presence of stoichiometric amounts of triphenylphosphine. The corresponding 9H-pyrrolo[1,2-a]indole products 36 were synthesized in good yields, with either electron-rich or electronwithdrawing groups on the indole backbone (13 examples, 51–88 % isolated yield). In this transformation, the substitution pattern of the indole substrate and the allenoate partners seems not to have a huge impact on the reaction outcome. Interestingly, this reaction could be extended to the use of α-substituted allenoates 37 (Scheme 8b). Indeed, ethyl 2-benzylbuta-
2,3-dienoate (R5 = Ph) and diethyl 2-vinylidenesuccinate (R5 =CO2Et) 37 gave the annulation products 38 in moderate to good yields (4 examples, 43–82 % yield). Only the ethyl 2-methylbuta-2,3-dienoate substrate (R5 = H) gave disappointing results (32 % yield). To simplify the purification step, it was emphasized that polymer-supported PPh3 could be used in this process (56 % yield). Unfortunately, up to now, the development of the catalytic version of this reaction failed, presumably because of the poor stability of the allenoate partner in the reaction conditions. Finally, a mechanism was proposed. After
the addition of the trivalent phosphine to the allenoate 35, the zwitterionic species D was formed. The latter was subsequently protonated by the N-H proton of the indole, to give the corresponding vinylphosphonium salt F. The addition of the conjugate base of the indole E to F furnished the ylide G, which undergoes an intramolecular Wittig reaction to form the 3Hpyrrolo[1,2-a]indole isomer H.
After isomerization, the stable 9H-isomer was isolated. Some research groups have developed simple transformations for the synthesis of pyrroloindole structure, with the use of Brønsted acid such as hydrochloric acid (Scheme 9a). Starting from 4,6-dimethoxy-3-methyl (or 3-aryl)-1H-indoles 39, in reaction with chalcone derivatives 40, the 9H-pyrrolo[1,2-a]indoles 41 are directly synthesized in good yields, after recrystallization from acetonitrile (18 examples, up to 95 % yield).[20] As expected, this reaction proceeds via a Michael addition of the indole C2-carbon to the chalcone double bond, followed by the addition of the nitrogen atom to form the pyrroloindole backbone, with the elimination of one molecule of water. Later on, Zu expanded this methodology by the use of α,-unsaturated ketone derivatives 43 and tryptamines or 3-methylindole substrates 42, in presence of catalytic amounts of p-TSA (ptoluenesulfonic acid) (Scheme 9b).[21] Numerous highly functionalized products 44 were easily obtained, in generally good yields (16 examples, 42–90 % yield). It was noticed that at 110 °C, this transformation could be catalyzed with other Brønsted acid or Lewis acid (such as FeCl3 or ZnCl2), albeit with lower yields.
9,9-Disubstituted 9H-pyrrolo[1,2-a]indoles 46 were also efficiently obtained via hydroiodic acid (HI) promoted (or catalyzed) cyclization of 1-[2-(1-arylvinyl)phenyl]-1H-pyrrole substrates 45 (Scheme 9c).[22] Alkyl-substituted substrates (R2 =Me) gave a lower yield in the desired compound, even using stoichiometric amounts of HI. This lower reactivity can be attributed to the less stabilized benzylic carbocation intermediate in the case of an alkyl substituent (R2 = Me), compared to the aryl moieties (R2 = Ar).
In 2018, the microwave-assisted condensation of 3Hindolium chloride salt 47 with 2.0 equiv. of pyridine or quinoline-carboxaldehyde derivatives, in acetic acid, led to the isolation of polysubstituted 9H-pyrrolo[1,2-a]indole-3-carboxamides 48 (5 examples, 60–76 % yield).[23] In the presence of piperidine, the dihydro-1H-imidazo[1,2-a]indol-2(3H)-one derivatives 49 were isolated in good yields (Scheme 10). The reaction of this compound in acidic media (glacial acetic acid at 100 °C using microwave heating) furnished the pyrroloindole product 50 in 74 % isolated yield. Furthermore, the reaction of 49 with pyridine-4-carboxaldehyde produced the highly functionalized product 51 in 80 % yield. Overall, this synthetic strategy gives straightforward access to highly functionalized 9H-pyrrolo-[1,2-a]indole-3-carboxamides. A careful NMR analysis of these new compounds and a tentative explanation of the different reaction pathways were proposed by the authors and resumed in Scheme 10.
During the studies on the formation of 3H-pyrrolo[1,2-a]-indole-2-carbaldehydes 55 using enantioselective organocatalytic methodologies, Enders and Wang independently found that the corresponding product isomerizes directly to furnish the most stable 9H-isomer 56 (Scheme 11).[24] This isomerization proceeds more particularly with the use of the furylacrolein substrate. The authors noticed that instead of the diphenylprolinol ether catalyst 53, pyrrolidine 54 could be used to catalyze the reaction. With the use of other aryl acroleins, if the 3Hisomer-products are enough stable in the air at room temperature and could be purified using silica gel chromatography, the isomerization into the 9H-isomer took place easily in CDCl3 at room temperature within one day. This transformation can even
be accelerated in presence of a strong acid such as p-TSA.
In 2017, Tang described an approach for the synthesis of the 9H-pyrrolo[1,2-a]indole backbone, based on a radical addition/cyclization/isomerization cascade process (Scheme 12a).[25a] Using NaI as a catalyst and tert-butyl hydroperoxide (TBHP) as an oxidant, different N-propargyl indoles 57 reacted smoothly with arylsulfonohydrazide (ArSO2NHNH2) derivatives 58 to furnish the corresponding 2-sulfonated-pyrroloindoles 59. If different iodine source (such as tetrabutylammonium iodide, KI and I2) could be used in this reaction, TBHP proved to be the best oxidant. The reaction scope was extended to more than 30 examples, including substitutions on different positions of the indole backbone and the propargyl functional groups. Interestingly, different sulfonohydrazide substrates were efficient in this transformation, forming in situ either alkyl or aryl sulfonyl radicals. The reaction mechanism started with the iodine-assisted decomposition of TBHP, which after reaction with the hydrazide generated a sulfonyl radical I. The addition of the latter on the N-propargyl group of the substrate 57 furnished the corresponding alkenyl radical J, which undergoes an intramolecular cyclization to form the pyrroloindole ring. After oxidation and isomerization steps, the desired 9H-isomer was delivered. In 2019, Wu, Qiu et al. reported another tandem radical process starting from 1-(prop-2-yn-1-yl)indoles 57, aryldiazonium tetrafluoroborates and sulfur dioxide surrogate of DABCO (1,4-diazabicyclo[2.2.2]octane) [DABCO·(SO2)2], for the synthesis of 9Hpyrrolo[1,2-a]indole derivatives 59 (Scheme 12b, 19 examples, 53–77 % yield).[25b] The mechanism remains globally the same as that previously described, namely the combination of DABCO·(SO2)2 with aryldiazonium tetrafluoroborates generates in situ the arylsulfonyl radical, which performs a radical addition on the alkyne of the substrate giving the corresponding alkenyl radical intermediate. Subsequently, an intramolecular addition occurs, followed by oxidation assisted by a tertiary amine radical cation, and then the deprotonation and tautomerization steps. To avoid the use of an excess amount of oxidant (such as TBHP), Zhang, Lin et al. developed a facile route for the synthesis of 2-sulfonated 9H-pyrrolo[1,2-a]indoles 59 via a photoredox-catalyzed cascade radical annulation of N-propargylindoles 57 and sulfonyl chlorides (Scheme 12c, 25 examples,
31–81 % yield).[25c] In this study, the activated arylsulfonyl radical species is generated from the combination of visible light and fac-Ir(bpy)3 as a photocatalyst.
Feldman reported an original thermal rearrangement of 2-(allenyl)phenyl azides 60 for the formation of 3H-pyrrolo[1,2-a]- indoles 62, which in most cases undergo isomerization to the most stable 9H-isomer 63 after purification on silica gel (Scheme 13).[26] During this thermolysis, the concomitant formation of the 1,4-dihydrocyclopenta[b]indole product 61 was always observed, with a ratio 61:62 of 2.7:1 to 1:1.5.
2.2. Organometallic-Promoted Reactions
2.2.1. Copper-Catalyzed Transformations
In 2016, Chen et al. developed a tandem Friedel-Crafts alkylation/annulation transformation, catalyzed by Cu(OTf)2(Scheme 14a).[27] The reaction of N-unprotected indole derivatives 64 with 1,2-dicarbonyl-3-enes 65 furnished the 9Hpyrrolo[1,2-a]indoles 66 in moderate to good isolated yields (31 examples, 38–87 % yield). This reaction occurred also in presence of AgOTf or Zn(OTf)2, albeit with lower yields (52 % and 69 % respectively). Only 3-substituted indoles (R2 = Me, allyl, 3-cyanomethyl) should be used in this reaction, presumably to promote the exclusive formation of the 9H-isomer of the pyrroloindole product. The proposed mechanism involves an intermolecular Friedel-Crafts alkylation, followed by the annulation reaction and an isomerization to finally deliver the 9H-pyrrolo[1,2-a]indole product.
Later, Zhang et al. described another Michael addition-condensation cascade reaction between α,-unsaturated ketimines 68 and 3-substituted indoles (Scheme 14b).[28] With 5 mol-% of CuBr2 as a catalyst, the reaction provides 9H-pyrrolo[1,2-a]indole derivatives 69 in moderate to good isolated yields (25 examples, 50–99 % yield). The reaction can also be carried out both with Lewis acids (FeCl3, 91 %) and Brønsted acids (TfOH, 82 %). It seems that many aryls on the ketamine partner are well tolerated (R3 and R4 groups) with good yields, even though no reaction occurs with a strong electron-withdrawing group such as R3 = 4-nitrophenyl. Moderate yields were obtained with 3-methylindoles bearing various substituents on the 4, 5, and 6-positions (R1 and R2 substituents). Here again, no substrate with R2 = H has been tested. A plausible mechanism begins with a Michael addition followed by an intramolecular nucleophilic addition and then an isomerization to provide the desired
product.
In 2017, copper(II) was also used by Zhu et al. in a tandem radical cyclization of diphenylphosphine oxide 71 with 1-(3-arylprop-2-yn-1-yl)-1H-indoles 70 (Scheme 15).[29] With the optimized conditions in hand (25 mol-% of CuSO4 as a catalyst and 2.0 equiv. of K2S2O8 as oxidant), a series of 2-phosphinoyl-9Hpyrrolo[1,2-a]indoles 72 was obtained in moderate yields (21 examples, 38–76 %). The outcomes of the reaction were not significantly affected by functional groups either on indoles (R1 and R2) or on the aryls linked to the alkyne. However, when dialkylphosphites were used, no reaction was detected. After some control experiments, a mechanism has been suggested which is initiated by addition of the P-centered radical [formed by the oxidation of Ar2P(O)H by CuII] on the alkyne, leading to a vinyl radical which then undergoes an intramolecular cyclization. After an oxidation step, the isomerization of 3H-isomer leads to 9H-pyrrolo[1,2-a]indole derivatives.
In 2017, Bu et al. described a Friedel-Crafts alkylation/cyclization with C3-substituted indoles 73 and aromatic aldehydederived oxodienes 74, catalyzed by Cu(OTf)2 (Scheme 16).[30] For this tandem reaction, this catalyst leads to a quantitative yield, while both Brønsted acid (TfOH, 81 % yield) and Lewis acid [Sc(OTf)3, 97 % yield] can be used. Several substrates were investigated to synthesize 9H-pyrrolo[1,2-a]indole derivatives 75 (20 examples, 59–88 %). It appeared that steric hindrance of substituents in para-position on the phenyl ring (Ar1) influenced the results, whereas, in meta-position on the same aryl group, the reaction outcome was affected by electronic effects. The reaction could work when R2 is different than a methyl group (CH2CO2Et, CH2CH2OH, ...). Concerning the mechanism, the first
step is a Friedel-Crafts alkylation followed by a 1,2-addition. After a dehydration step, isomerization occurs.
In the continuity of their previous work, Bu et al. extended their methodology to 3-arylcarbonylcoumarins 77 to increase the structural complexity of 9H-pyrrolo[1,2-a]indoles 78 (21 examples, 34–99 %) (Scheme 17).[31] The mechanism remains globally the same, while only 3-methyl indole seems to be a suitable partner. Additionally, the yields drop when R2 is different than a phenyl group, and the reaction can tolerate a wide range of R1 substituents. It seems that electron-withdrawing groups improve the reactivity of the corresponding substrates. A Suzuki cross-coupling post-functionalization has been developed to obtain more complex pentacyclic core, in good yields.
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1-[3-(trifluoromethyl)phenyl]piperidin-4-amineCatalog No.:AA01A931 CAS No.:1016864-56-4 MDL No.:MFCD09945528 MF:C12H15F3N2 MW:244.2561 |
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2-[4-(prop-2-ynamido)phenyl]acetic acidCatalog No.:AA01AURQ CAS No.:1016865-10-3 MDL No.:MFCD09945626 MF:C11H9NO3 MW:203.1941 |
3-(5-Methyl-2-nitrophenoxy)propanoic acidCatalog No.:AA019MT5 CAS No.:1016865-66-9 MDL No.:MFCD09948263 MF:C10H11NO5 MW:225.1980 |
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4-(prop-2-ynamido)benzoic acidCatalog No.:AA01AUPV CAS No.:1016868-07-7 MDL No.:MFCD09946029 MF:C10H7NO3 MW:189.1675 |
[(3-Phenylpropyl)sulfonyl]acetic acidCatalog No.:AA019N8X CAS No.:1016870-51-1 MDL No.:MFCD09950402 MF:C11H14O4S MW:242.2915 |
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2-(propan-2-yloxy)ethanethioamideCatalog No.:AA01B3X0 CAS No.:1016885-92-9 MDL No.:MFCD09938263 MF:C5H11NOS MW:133.2119 |
2-(3-Acetylphenoxy)-n,n-dimethylacetamideCatalog No.:AA019XKD CAS No.:1016886-24-0 MDL No.:MFCD09949855 MF:C12H15NO3 MW:221.2524 |
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2-(3-ethylphenoxy)pyridine-4-carbonitrileCatalog No.:AA01A91G CAS No.:1016887-17-4 MDL No.:MFCD09938425 MF:C14H12N2O MW:224.2579 |
5-Bromo-n-ethyl-2-fluorobenzamideCatalog No.:AA00H9H2 CAS No.:1016887-98-1 MDL No.:MFCD09938532 MF:C9H9BrFNO MW:246.0763 |
6-(propan-2-yloxy)pyridine-3-carbothioamideCatalog No.:AA01BF2U CAS No.:1016888-06-4 MDL No.:MFCD09942730 MF:C9H12N2OS MW:196.2694 |
4-[(2-Methoxyethane)sulfonyl]benzoic acidCatalog No.:AA01A7Z3 CAS No.:1016888-12-2 MDL No.:MFCD09942739 MF:C10H12O5S MW:244.2643 |
2-chloro-N-(pentan-3-yl)propanamideCatalog No.:AA019KMX CAS No.:1016888-28-0 MDL No.:MFCD09942776 MF:C8H16ClNO MW:177.6717 |
2-[4-(Pyridin-4-yl)-1,3-thiazol-2-yl]acetonitrileCatalog No.:AA00H9H3 CAS No.:1016888-78-0 MDL No.:MFCD09950233 MF:C10H7N3S MW:201.2477 |
3-(3-bromophenoxymethyl)pyridineCatalog No.:AA019N4Z CAS No.:1016889-14-7 MDL No.:MFCD09942891 MF:C12H10BrNO MW:264.1179 |
2-Bromo-4-fluoro-1-propoxybenzeneCatalog No.:AA00054I CAS No.:1016889-72-7 MDL No.:MFCD09940143 MF:C9H10BrFO MW:233.0775 |
(R)-Pentan-2-amine hydrochlorideCatalog No.:AA01DU2W CAS No.:101689-05-8 MDL No.:MFCD28501705 MF:C5H14ClN MW:123.6244 |
2-[(3-methoxyphenyl)methoxy]propanoic acidCatalog No.:AA019N30 CAS No.:1016890-44-0 MDL No.:MFCD09935962 MF:C11H14O4 MW:210.2265 |
6-[4-(4-Fluorophenyl)piperazin-1-yl]pyridine-3-carbonitrileCatalog No.:AA019TRN CAS No.:1016891-05-6 MDL No.:MFCD09936073 MF:C16H15FN4 MW:282.3155 |
1-[(2-Aminoethyl)sulfanyl]-2-fluorobenzeneCatalog No.:AA01AI36 CAS No.:1016891-91-0 MDL No.:MFCD09936291 MF:C8H10FNS MW:171.2351 |
[1,1'-Biphenyl]-2,2'-disulfonic acid,4,4'-bis[(2-hydroxy-1-naphthalenyl)azo]-, disodium saltCatalog No.:AA01DPZX CAS No.:10169-02-5 MDL No.:MFCD00004072 MF:C32H20N4Na2O8S2 MW:698.6327 |
5-Bromo-2-hydroxy-3-nitrobenzoic acidCatalog No.:AA000554 CAS No.:10169-50-3 MDL No.:MFCD00463872 MF:C7H4BrNO5 MW:262.0144 |
4-Acetyldiphenyl sulfideCatalog No.:AA000552 CAS No.:10169-55-8 MDL No.:MFCD00026227 MF:C14H12OS MW:228.3095 |
(Tetrahydropyran-4-yl)methyl tosylateCatalog No.:AA00055U CAS No.:101691-65-0 MDL No.:MFCD09475806 MF:C13H18O4S MW:270.3446 |
4-(Iodomethyl)tetrahydro-2H-pyranCatalog No.:AA00055T CAS No.:101691-94-5 MDL No.:MFCD06410724 MF:C6H11IO MW:226.0554 |
2-[benzyl(methyl)amino]propanoic acidCatalog No.:AA01AJE3 CAS No.:101692-94-8 MDL No.:MFCD01463743 MF:C11H15NO2 MW:193.2423 |
2,4-Imidazolidinedione, 5-methyl-5-phenyl-, (5R)-Catalog No.:AA00055J CAS No.:101693-73-6 MDL No.:MFCD20727962 MF:C10H10N2O2 MW:190.1986 |
tert-Butyl ((1R,2R)-2-aminocyclopentyl)carbamateCatalog No.:AA00055B CAS No.:1016971-66-6 MDL No.:MFCD11040591 MF:C10H20N2O2 MW:200.2780 |
3-Benzyloxy-4-iodo-5-nitro-benzaldehydeCatalog No.:AA000559 CAS No.:1016976-13-8 MDL No.:MFCD19441863 MF:C14H10INO4 MW:383.1380 |
3-Fluoro-5-methoxycarbonylphenylboronic acid, pinacol esterCatalog No.:AA000557 CAS No.:1016979-31-9 MDL No.:MFCD12546616 MF:C14H18BFO4 MW:280.0997 |
2-Phenyl-1-(pyridin-4-yl)ethan-1-oneCatalog No.:AA0094HQ CAS No.:1017-24-9 MDL No.:MFCD12153293 MF:C13H11NO MW:197.2325 |
1-[(4-aminophenyl)methyl]-1,2-dihydropyridin-2-oneCatalog No.:AA019UYZ CAS No.:1017-42-1 MDL No.:MFCD09048642 MF:C12H12N2O MW:200.2365 |
1-[(3-aminophenyl)methyl]-1,2-dihydropyridin-2-oneCatalog No.:AA01A9MN CAS No.:1017-51-2 MDL No.:MFCD09804296 MF:C12H12N2O MW:200.2365 |
Di-p-tolylphosphineCatalog No.:AA00056F CAS No.:1017-60-3 MDL No.:MFCD01630843 MF:C14H15P MW:214.2427 |
Phosphonium, dimethyldiphenyl-, iodide (1:1)Catalog No.:AA00056B CAS No.:1017-88-5 MDL No.:MFCD04115089 MF:C14H16IP MW:342.1551 |
Chromium, trichlorotris(tetrahydrofuran)-Catalog No.:AA000567 CAS No.:10170-68-0 MDL No.:MFCD00013222 MF:C12H24Cl3Cr2O3+++ MW:426.6684 |
Manganese(0) carbonylCatalog No.:AA000566 CAS No.:10170-69-1 MDL No.:MFCD00011115 MF:C10Mn2O10 MW:389.9771 |
3-Amino-4-methyl-n-(2,2,2-trifluoroethyl)benzamideCatalog No.:AA019UJQ CAS No.:1017019-26-9 MDL No.:MFCD09938673 MF:C10H11F3N2O MW:232.2023 |
1-Amino-n-(propan-2-yl)cyclohexane-1-carboxamideCatalog No.:AA019WLF CAS No.:1017019-29-2 MDL No.:MFCD09938693 MF:C10H20N2O MW:184.2786 |
2-methyl-1-{[1,2,4]triazolo[4,3-a]pyridin-3-yl}propan-1-amineCatalog No.:AA01A99P CAS No.:1017019-83-8 MDL No.:MFCD09942655 MF:C10H14N4 MW:190.2450 |
2-(3-bromobenzamido)-4-fluorobenzoic acidCatalog No.:AA019N7F CAS No.:1017020-32-4 MDL No.:MFCD09938931 MF:C14H9BrFNO3 MW:338.1286 |
2-(3-bromophenoxy)-N-methylacetamideCatalog No.:AA019UQ5 CAS No.:1017020-76-6 MDL No.:MFCD09938982 MF:C9H10BrNO2 MW:244.0852 |
1-(Cyclobutylcarbonyl)piperidin-4-oneCatalog No.:AA00055Z CAS No.:1017021-42-9 MDL No.:MFCD09951084 MF:C10H15NO2 MW:181.2316 |
3-(4-ethyl-2,3-dioxopiperazin-1-yl)propanenitrileCatalog No.:AA019LL8 CAS No.:1017021-83-8 MDL No.:MFCD09942989 MF:C9H13N3O2 MW:195.2184 |
[1-(2,2,2-trifluoroethyl)pyrrolidin-3-yl]methanamineCatalog No.:AA019UTA CAS No.:1017022-18-2 MDL No.:MFCD09939124 MF:C7H13F3N2 MW:182.1867 |
N'-hydroxy-6-(piperidin-1-yl)pyridine-3-carboximidamideCatalog No.:AA019XM6 CAS No.:1017022-80-8 MDL No.:MFCD09939229 MF:C11H16N4O MW:220.2709 |
4-(morpholin-4-ylmethyl)benzene-1-carboximidamideCatalog No.:AA01ELLH CAS No.:1017023-23-2 MDL No.:MFCD09939326 MF:C12H17N3O MW:219.2829 |
6-[(prop-2-en-1-yl)amino]pyridine-3-carbonitrileCatalog No.:AA01FLWV CAS No.:1017023-76-5 MDL No.:MFCD09936460 MF:C9H9N3 MW:159.1879 |
4-(but-3-yn-1-yloxy)benzoic acidCatalog No.:AA01A634 CAS No.:1017024-01-9 MDL No.:MFCD09939454 MF:C11H10O3 MW:190.1953 |
N-(2,2,2-trifluoroethyl)cyclopentanamineCatalog No.:AA0198RT CAS No.:1017024-34-8 MDL No.:MFCD09936569 MF:C7H12F3N MW:167.1721 |
2-[(2-Ethylcyclohexyl)oxy]acetic acidCatalog No.:AA01ACBG CAS No.:1017026-13-9 MDL No.:MFCD09951036 MF:C10H18O3 MW:186.2481 |
2-chloro-N-(5-fluoro-2-methylphenyl)propanamideCatalog No.:AA019KMT CAS No.:1017026-21-9 MDL No.:MFCD09947184 MF:C10H11ClFNO MW:215.6518 |
4-(propan-2-yloxy)butanoic acidCatalog No.:AA01A6AC CAS No.:1017026-56-0 MDL No.:MFCD09944713 MF:C7H14O3 MW:146.1843 |
1-Amino-n-propylcyclohexane-1-carboxamideCatalog No.:AA01A9C5 CAS No.:1017027-29-0 MDL No.:MFCD09940938 MF:C10H20N2O MW:184.2786 |
2-Cyclopropylbenzo[d]oxazol-5-amineCatalog No.:AA00055Y CAS No.:1017027-77-8 MDL No.:MFCD09947485 MF:C10H10N2O MW:174.1992 |
2-(4-Ethylpiperazino)isonicotinonitrileCatalog No.:AA00948Y CAS No.:1017028-13-5 MDL No.:MFCD09947517 MF:C12H16N4 MW:216.2822 |
N-(piperidin-3-ylmethyl)aminosulfonamideCatalog No.:AA019UH5 CAS No.:1017029-06-9 MDL No.:MFCD09943817 MF:C6H15N3O2S MW:193.2672 |
2-Bromo-n-(2,5-dichlorophenyl)-3-methylbutanamideCatalog No.:AA019MLQ CAS No.:1017029-14-9 MDL No.:MFCD09937374 MF:C11H12BrCl2NO MW:325.0291 |
[Methyl(pyridin-3-ylsulfonyl)amino]acetic acidCatalog No.:AA019MZ6 CAS No.:1017029-42-3 MDL No.:MFCD09937432 MF:C8H10N2O4S MW:230.2410 |
2-bromo-3-methyl-1-(1,2,3,4-tetrahydroisoquinolin-2-yl)butan-1-oneCatalog No.:AA019KWG CAS No.:1017030-81-7 MDL No.:MFCD09949239 MF:C14H18BrNO MW:296.2028 |
6-(2-Bromophenoxy)pyridine-3-carboxylic acidCatalog No.:AA019V82 CAS No.:1017031-07-0 MDL No.:MFCD09937687 MF:C12H8BrNO3 MW:294.1008 |
2-(propan-2-yloxy)benzene-1-carbothioamideCatalog No.:AA019WH1 CAS No.:1017031-17-2 MDL No.:MFCD06761746 MF:C10H13NOS MW:195.2813 |
1-propyl-1H-pyrrole-2-carboxylic acidCatalog No.:AA019V1M CAS No.:1017031-23-0 MDL No.:MFCD09951771 MF:C8H11NO2 MW:153.1784 |
[1-(2-methoxyphenyl)ethyl](propyl)amineCatalog No.:AA019LN4 CAS No.:1017031-66-1 MDL No.:MFCD09948156 MF:C12H19NO MW:193.2854 |
6-(4-Hydroxypiperidin-1-yl)pyridine-3-carbonitrileCatalog No.:AA01BBC7 CAS No.:1017034-18-2 MDL No.:MFCD09942367 MF:C11H13N3O MW:203.2404 |
1-(2-bromo-3-methylbutanoyl)piperidine-3-carboxamideCatalog No.:AA019KWW CAS No.:1017034-24-0 MDL No.:MFCD09942383 MF:C11H19BrN2O2 MW:291.1848 |
(3-ethynylphenyl)ureaCatalog No.:AA019TY6 CAS No.:1017034-89-7 MDL No.:MFCD09938578 MF:C9H8N2O MW:160.1726 |
4-fluoro-3-(methoxymethyl)benzonitrileCatalog No.:AA01B3U1 CAS No.:1017035-13-0 MDL No.:MFCD09938614 MF:C9H8FNO MW:165.1643 |
3-(Morpholine-4-carbonyl)benzonitrileCatalog No.:AA00H9H6 CAS No.:1017035-26-5 MDL No.:MFCD09942561 MF:C12H12N2O2 MW:216.2359 |
1-amino-N-(4-bromophenyl)cyclohexane-1-carboxamideCatalog No.:AA01AHR6 CAS No.:1017035-47-0 MDL No.:MFCD09942615 MF:C13H17BrN2O MW:297.1909 |
ethyl 2-(4-carbamothioylphenoxy)acetateCatalog No.:AA019TWZ CAS No.:1017036-46-2 MDL No.:MFCD09936031 MF:C11H13NO3S MW:239.2908 |
Benzenepropanenitrile, 4-(difluoromethoxy)-β-oxo-Catalog No.:AA00055W CAS No.:1017036-63-3 MDL No.:MFCD09936058 MF:C10H7F2NO2 MW:211.1649 |
1-(4-ethylphenyl)piperidin-4-amineCatalog No.:AA019Y3K CAS No.:1017036-75-7 MDL No.:MFCD11204140 MF:C13H20N2 MW:204.3113 |
2-[4-(pyridin-2-ylmethoxy)phenyl]acetonitrileCatalog No.:AA019UOK CAS No.:1017037-58-9 MDL No.:MFCD09950290 MF:C14H12N2O MW:224.2579 |
4,5-Dimethoxy-2-(prop-2-ynamido)benzoic acidCatalog No.:AA01C38K CAS No.:1017038-09-3 MDL No.:MFCD09950374 MF:C12H11NO5 MW:249.2194 |
N-benzyl-2-cyano-N-methylacetamideCatalog No.:AA01B1LI CAS No.:1017040-87-7 MDL No.:MFCD09947110 MF:C11H12N2O MW:188.2258 |
1-(2-ethylphenyl)piperidin-4-amineCatalog No.:AA01A7WL CAS No.:1017042-50-0 MDL No.:MFCD09939598 MF:C13H20N2 MW:204.3113 |
[1-(3-Bromophenyl)pyrrolidin-3-yl]methanamineCatalog No.:AA019X9I CAS No.:1017043-63-8 MDL No.:MFCD09939797 MF:C11H15BrN2 MW:255.1542 |
6-(4-fluorophenoxy)-N'-hydroxypyridine-3-carboximidamideCatalog No.:AA01A7G3 CAS No.:1017043-73-0 MDL No.:MFCD09951166 MF:C12H10FN3O2 MW:247.2251 |
2-bromo-N-(2,3-dimethylphenyl)-3-methylbutanamideCatalog No.:AA019KVZ CAS No.:1017044-59-5 MDL No.:MFCD09944887 MF:C13H18BrNO MW:284.1921 |
tert-Butyl 3-{[(benzyloxy)carbonyl]amino}azetidine-1-carboxylateCatalog No.:AA0098WV CAS No.:1017044-94-8 MDL No.:MFCD09944986 MF:C16H22N2O4 MW:306.3569 |
2-methyl-4-(1,3,4-oxadiazol-2-yl)anilineCatalog No.:AA019UK2 CAS No.:1017045-81-6 MDL No.:MFCD09947647 MF:C9H9N3O MW:175.1873 |
5-Benzoxazolamine, 2-(1,1-dimethylethyl)-Catalog No.:AA00056O CAS No.:1017046-27-3 MDL No.:MFCD09947725 MF:C11H14N2O MW:190.2417 |
