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Research Articles Various Synthetic Methods Using Aromatic Carboxylic Various Synthetic Methods Using Aromatic Carboxylic Anhydrides Isamu Shiina Faculty of Science, Tokyo University of Science 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601 Abstract With regards to carbon-hydrogen bonds formation, owing to progress in asymmetric hydrogenation reactions, etc., optically As a result of pursuing dehydrating condensation reagents, active molecules with their absolute configurations controlled which can be stably stored at room temperatures, easy to handle, have been obtained. However, compared to the remarkable and highly reactive, it was found that aromatic carboxylic advances in the studies of (1) and (2), there has been no anhydrides can be used as versatilely highly functional reagents. significant progress until now in the development of novel Reaction by using TFBA or BTFBA with a Lewis acid catalyst reactions forming (3) and (4). Under these situations, we tried to can be one of the most powerful protocols for carbon-oxygen discover a series of efficient novel carbon-hetero element bonds bond formation, which enable the synthesis of the desired forming reactions by using “aromatic carboxylic anhydrides” carboxylic esters and lactones in good yields. Furthermore, as condensation reagents. Since these reactions proceed under the use of MNBA or DMNBA with a nucleophilic catalyst mild conditions without using harmful substances, such as under basic conditions enables convenient preparation of acid- heavy-metal salts, they are flexible methods for the synthesis sensitive carboxylic esters, lactones, and amides. In addition, the of molecules with less environmental burden and can form use of PMBA or benzoic anhydride with an asymmetric catalyst the carbon-hetero element bond at any desired position with realizes the kinetic resolution of racemic secondary alcohols and high selectivity. In the present article, we introduce a series racemic 2-arylpropionic acids, resulting in the establishment of of our research results, which have been performed over the a novel synthetic method for optically active carboxylic esters, past several years covering the range from development to the secondary alcohols, and 2-arylpropionic acids. applications. 1. Introduction 2. Discovery of the condensation reaction using “aromatic carboxylic anhydrides” To synthesize organic substances efficiently in an artificial way, it is required to develop convenient methods for forming While researching the chemistry of silyl enol ethers, we (1) carbon-carbon bonds; (2) carbon-hydrogen bonds; (3) studied on silyl esters of carboxylic acids and focused on their carbon-oxygen bonds; and (4) carbon-nitrogen bonds with high effectiveness as acylating reagents. First, we discovered a novel selectivities. With a rapid advancement of organic synthesis reaction, wherein, in the presence of a Lewis acid catalyst, a over the past twenty years, more and more excellent chemical nucleophilic substitution reaction occurs between carboxylic conversion methods have been developed. The establishment silyl esters (electrophile) and an alkyl silyl ether (nucleophile) to of the “acyclic stereocontroled synthesis”, such as the allylation afford the corresponding carboxylic ester in high yield (Scheme reaction or the aldol reaction, which forms carbon-carbon bonds 1).1 However, this reaction is a direct transesterification of a with regio- and stereoselectivity, made it possible to build carboxylic silyl ester to a carboxylic ester required heat with a the basic carbon framework of complex organic molecules process of transformation of a siloxy group to an alkoxy group. possessing molecular weights of over 1,000 in recent years. SiCl2(OTf)2 R1 OTMS (2 mol%) R1 OR2 + R2OTMS O TMS2O O (1.1 eq.)(1.0 eq.) 60 °C, 20 h 97% 1 R = Ph(CH2)2 2 R = Ph(CH2)3 Scheme 1 2 At this stage, we decided to reinvestigate an alternative silyl ether must attack preferentially the aliphatic acyl moiety to method for the preparation of carboxylic esters using different afford the corresponding aliphatic carboxylic ester along with reagents under milder conditions. the elimination of aromatic carboxylic silyl ester. Acetyl chloride and benzoyl chloride, for example, In fact, when trimethylsilyl ether of 4-phenyl-2-butanol are frequently used for the acylation of alcohol, and acetic was added to a mixed anhydride prepared in advance from anhydride is also used as a reagent suitable for acetylation. On acetic acid trimethylsilyl ester and benzoic anhydride by using the other hand, aromatic carboxylic anhydrides have especially TiCl2(ClO4)2 as a Lewis acid catalyst, the desired ester A was poor reactivity, therefore, they are rarely used for the direct obtained in 90% yield, along with the undesired ester B (1%) benzoylation of alcohol. Thus, we assumed that with the less generated by the direct reaction of benzoic anhydride and the reactive property of benzoic anhydride as an acyl donor, the trimethylsilyl ether (Table 1, Entry 1). The result revealed that corresponding aliphatic carboxylic esters can be selectively in the first stage of the reaction, conversion to mixed anhydride obtained from aliphatic carboxylic silyl esters and alkyl silyl from benzoic anhydride proceeded smoothly, and the formation ethers (Scheme 2). rate of benzoic ester was much slower than that of aliphatic First, an acyl transfer reaction proceeds smoothly between acid ester. When the same experimental procedure using other aliphatic carboxylic silyl esters and aromatic carboxylic anhydrides available was carried out, interesting results were anhydrides. Next, part of the mixed anhydride generated rapidly obtained as described in Entries 2–4. Though pivalic anhydride disproportionates into two kinds of symmetrical acid anhydrides, or trifluoroacetic anhydride are useful reagents for preparing therefore, three kinds of acid anhydrides in total must be rapidly mixed anhydrides in peptide synthesis, they are not suitable for put in the equilibrium mixture state in the reaction system. Since this condensation reaction. For example, in the reaction using the reactivity of acid anhydrides in general becomes higher the anhydrides, a considerable amount of the undesired esters B in the order of symmetrical aromatic carboxylic anhydride < (pivalic ester or trifluoroacetic ester) is unexpectedly generated symmetrical aliphatic carboxylic anhydride < mixed anhydride, as a byproduct (Entries 2 and 3). On the other hand, as Entry it is assumed that the most reactive mixed anhydride will react 4 shows, the transesterification of pivalic acid trimethylsilyl preferentially with a nucleophile. Furthermore, if the reactivity ester using benzoic anhydride afforded A in excellent yield, of the aliphatic carboxylic acid moiety in the mixed anhydride is which revealed that aliphatic acid esters are in general formed higher than that of the aromatic carboxylic acid moiety, an alkyl preferentially over benzoic esters under the conditions. Ar O Ar 2 R1 OTMS O O R1 O Ar R OTMS R1 OR2 O MXn O O MXn O CH2Cl2, rt CH2Cl2, rt –ArCOOTMS –ArCOOTMS R1 O R1 Ar O Ar + O O O O Scheme 2 R3 O R3 O O R1 OTMS (1.1 eq.) R1 OR2 R3 OR2 + R2OTMS + O O O TiCl2(ClO4)2 (1.1 eq.)(1.0 eq.) (20 mol%) AB CH2Cl2, rt 2 R = Ph(CH2)2CHCH3 Entry R1 R3 Yield of A / % Yield of B / % 1 Me Ph 90 1 2 Me tBu 30 47 3 Me CF3 39 23 4 tBu Ph 89 4 Table 1 3 3. Esterification reaction using 4-trifluoromethyl enhances the chemoselectivity. In particular, the reaction using benzoic anhydride (TFBA)2 4-trifluoromethylbenzoic anhydride (TFBA) afforded almost perfect selectively of the desired aliphatic carboxylic ester with In order to develop synthetic methods applicable to intra- no generation of benzoic ester by NMR detection. Furthermore, molecular condensation, it is required to design synthetic as Entries 2 and 3 show, the introduction of chlorine to the protocols giving the target products in high yields from nearly 2-position of the aromatic ring produced the same or a little less equimolar amounts of two starting materials. Furthermore, selectivity. On the other hand, in the case of using substituted for the purpose of enhancing the yields of cyclized products, benzoic anhydrides possessing a methoxy or a methyl group, it is essential to develop a novel synthetic method for esters the selectivities were reversed, affording preferentially the with perfect chemoselectivity. Thus, we tried to increase undesired benzoic esters over the desired aliphatic carboxylic both the yield and chemoselectivity by introducing various esters (Entries 7–10). From these results, it was found that the substituents on aromatic rings in the dehydrating condensation introduction of a strong electron-withdrawing group to the reagents (Table 2). For example, comparing Entry 1 with 4-position of an aromatic ring was effective; in particular, TFBA Entries 4–6 shows that the introduction of an electron- with a trifluoromethyl group functioned best as a condensation withdrawing group to the 4-position of the aromatic ring reagent. X X n O n O O 1 (1.1 eq.) 1 2 R OTMS R OR Xn 2 + R2OTMS + OR O TiCl (ClO ) O 2 4 2 O (1.1 eq.)(1.0 eq.) (20 mol%) AB CH2Cl2, rt 1 R = Ph(CH2)2 2 R = Ph(CH2)3 Entry Xn Yield / % A / B 1 H 98 16 / 1 2 2-Cl 89 13 / 1 3 2,6-Cl2 68 3.5 / 1 4 4-Cl 60 32 / 1 5 4-F 93 49 / 1 6 4-CF3 91 >200 / 1 7 4-MeO 95 1 / 1.6 8 2-MeO 91 1 / 24 9 2-Me 90 1 / 1.8 10 2,6-Me2 97 1 / 32 Table 2 R1 OTMS TFBA R1 OR2 + R2OTMS O O Sn(OTf)2 (1.1 eq.)(1.0 eq.) (1-10 mol%) or R1 = Me, iPr, iBu, tBu, [TiCl2(OTf)2] Ph(CH ) 2 2 CH2Cl2, rt 2 R = Ph(CH2)3, 92-99% Ph(CH2)2CHCH3 F3C CF3 O O O 4-Trifluoromethylbenzoic Anhydride (TFBA) Scheme 3 4 Next, we examined the versatility of this esterification 4.
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