蒽醌类化合物的合成研究进展

蒽醌是自然界中非常重要的一类醌类化合物，具有抗菌、抗癌、止血、防氧化等多种生物活性，受到药物学家及相关工作者的特别关注。本文综述了近年来这类化合物的合成方法，重点介绍了Friedel-Crafts反应、Michael 反应、Diels-Alder反应、Heck反应、羰-烯反应、蒽环氧化反应等在蒽醌骨架构筑过程中的研究进展。最后对这类方法中存在的问题进行了讨论，并对未来的发展进行了展望。     

Regiospecific Construction of Polyoxygenated 9,10-Anthraquinones. Total Synthesis of Islandicin and Digitopurpone

Current interest³ in a practical synthesis of the antibiotic adriamycin⁴ 1 prompts us to report some consequences of the photochemical⁵ versus the Friedel-Crafts⁶ approaches in the construction of unsymmetrical polyhydroxy-anthraquinones. These two complementary methods have now been exploited in the preparation of the natural coloring matters islandicin,⁷ 2, and digitopurpone,⁸ 3.     

Regioselective Synthesis of Ellipticine

An eight‐step synthesis of the tetracyclic pyridocarbazole alkaloid ellipticine (= 5,11‐dimethyl‐6H‐pyrido[4,3‐b]carbazole; 1a ) in an overall yield of 13% is reported, starting from 4,7‐dimethyl‐1H‐indene. Key steps were iodination, Suzuki coupling, reductive cyclization, DDQ oxidation, and heterocyclization under loss of H₂O.     

二羟基蒽醌磷酰化衍生物的合成及表征

分别以4种不同位取代的二羟基葸醌和亚磷酸二乙酯或亚磷酸二丙酯为原料,通过简化的Atheron-Todd合成法合成了一系列二羟基葸醌的磷酰化衍生物,并通过量化计算对葸醌上不同羟基电荷分布进行了研究,发现β-羟基氧上的电荷密度大于β-羟基氧上的电荷密度.所合成化合物的结构均经IR,MS,1H NMR,31p NMR和元素分析确证,并通过荧光猝灭法初步探讨了部分新化合物的生物活性.     

Regioselective Synthesis of Flindersine Analogues

6-Alkylpyrano [3,2-c] quinolin-5(2H)-ones(11a-e) were obtained in excellent yields by simply refluxing propynyl and butymyl ethers (6) of 4-hydroxy-1-alkylquinolin-2H-ones (2) in chlorobenzene for 10h, 5-Prop-2-ynyloxy-2H-pyrano [3,2-c] quinoline (12) was also obtained from the thermal rearrangement of 2,4-bis prop-2-ynyloxyquinoline (4).     

定位选择合成柠檬酸月桂醇单酯

定位选择合成柠檬酸月桂醇单酯;淀粉;催化氧化;胶粘性     

Regioselective Synthesis of N-Alkyl Pyridones

The regioselective synthesis of N-alkyl pyridones can be facilitated by alkylation of 2-methoxypyridines with activated halides. The syntheses are facile and high yielding with no traces of 2-alkoxypyridines.     

Regioselective Synthesis of Multi-substituted Phenylselenomethyl Isoxazolines

A mild, regioselective 1, 3-dipolar cycloaddition protocol for the preparation ofphenylselenomethyl isoxazolines through substituted allyl phenyl selenides and nitrile oxides wasreported.     

Regioselective Synthesis of 1,3,5-Trisubstituted Pyrazoles

Abstract

A new and a simple approach toward synthesis of 1,3,5-trisubstituted pyrazoles from chalcone arylhydrazones via oxidative cyclization has been achieved. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone was successfully used as an oxidizing agent to give excellent yields of pyrazoles.     

蔗糖酯的酶催化区域选择性合成

酶可以区域选择性地合成蔗糖酯，枯草杆菌等蛋白酶被用来区域选择性合成 1'-O-蔗糖酯，且通常不接受长链（大于C_(12))脂肪酸作为酰基授体，而脂肪酶可 催化宽范围的脂肪酸，除了脂肪酶和蛋白酶外，研究发现抗体酶也能区域和立体选 择地酰化蔗糖。蔗糖二酯、线型蔗糖酯都可以通过酶催化区域选择性地合成。酶催 化合成蔗糖酯通常在二甲基甲酰胺、二甲基亚砜和吡啶等有毒溶剂中进行。近几年 来，无溶剂条件下酶催化合成蔗糖酯，以及用叔丁醇等毒性较小的溶剂代替毒性较 大的溶剂的研究，也越来越受重视。     

Orthobromodiphenylmethane Derivatives as Starting Materials for the Total Synthesis of Anthraquinones

In this communication we describe the synthesis of four simple anthraquinones by a five-step sequence, using easily available bromobenzaldehydes and phenyllithium derivatives as starting materials.     

Regioselective Synthesis of Benzimidazolic Bioisosteres of Melatonin

A convenient synthesis of benzimidazolic bioisosteres of melatonin is described through a regioselective synthesis of 1,6-disubstituted benzimidazoles.     

Regioselective Synthesis of Carbazole Precursor to Olivacine

A short regioselective synthesis of ethyl 1 - methyl - 9H - carbazole - 3 - carboxylate is described from 3 - formylindole which utilizes Wittig reaction and Pd-C catalysed ring annulation reaction.     

Regioselective Synthesis of New Bibracchial Lariat Ethers

A practical and regioselective synthetic method for the synthesis of cis‐diastereomers of bibracchial lariat ethers (BiBLEs) bearing ester and amide groups is reported. The novel BiBLEs 3a and 4a–e with neutral side arms were prepared by reaction of the corresponding aza‐crown macrocycles 1a – c with ethylchlroacetate and chloroacetamide. The structures of the new compounds have been confirmed by FTIR, ¹H, ¹³C, DEPT, and MS spectroscopy.     

Regioselective Synthesis of Two Novel 2-geranyloxyacetophenones

The phenols containing geranyl units¹ are a large group of interesting natural products exhibited many physiological actions as antiflammatory, antibacterial and antioxidative activities². Two novel acetophenones 1 and 2 were recently isolated from the fruits of Evodia merrillii, a small folk medicinal tree widely distributed in Taiwan³. Their structures were elucidated as 2-(1'-geranyl)-4,6-dihydroxyacetophenone 1 and 2-(1'-geranyloxy)-2,6,α-trihydroxyacetophenone 2 by means of spectroscopic data. So far as we know, the total synthesis of them have not been reported yet. Herein, we wish to report the first total synthesis of 1 and 2,starting from 2,4,6-trihydroxyacetophenone.     

Regioselective Synthesis of Nanographenes by Photochemical Cyclodehydrochlorination

Novel nanographenes were prepared by a photochemical cyclodehydrochlorination (CDHC) reaction. Chlorinated precursors were irradiated in acetone in the presence of a base or in pure benzene and underwent multiple (up to four) regioselective cyclization reactions to provide rigid π‐conjugated molecules. Pure compounds were recovered in good yields by simple filtration at the end of the reaction. The CDHC reaction showed compatibility with both electron‐poor and electron‐rich substrates, thus allowing the synthesis of pyridine‐ and thiophene‐fused nanographenes. It also enabled the synthesis of sterically hindered contorted π‐conjugated molecules without causing full aromatization. A kinetic study showed that the CDHC reaction under the conditions used is a very fast process, and some reactions are completed within minutes. The CDHC reaction thus shows great potential as an alternative to other reactions involving harsher conditions for the preparation of nanographenes.     

Temporary Protection and Activation in the Regioselective Synthesis of Saccharide Sulfates

Regioselective sulfation with Et₃N · SO₃ of partially protected or unprotected glycosides via stannanediyl acetals or stannyl ethers, combined with persistent or temporary protecting groups is described. Stannylation of phenylboronates, followed by sulfation and aqueous workup, is an efficient way for the synthesis of monosulfated monosaccharides. The stannanediyl acetal 2 led in high yields to 3a , while sulfation of the diol 1 proceeded more slowly and led in lower yield to a mixture 1/3a/4a/5a (Scheme 1). The trehalose disulfate 8a was obtained in high yields from 7 ; reducing the amount of sulfating agent led to a mixture 6/8a/9a . Stannylation and sulfation of the galactoside 11 afforded 13a , while direct sulfation of 11 gave a mixture of the 2-and 3-sulfates 13a/14a besides some disulfate 15a . Sulfation of the lactose derivative 16 and the stannanediyl acetal 17 gave the 3-sulfate 18a , with some disulfate 19a being formed from 16 . The mannopyranoside 21 was selectively sulfated at OH–C(2), leading to 22a , while the corresponding diol 20 yielded mostly the isomer 23a and some disulfate 24a . Sulfation of the stannyl ethers derived from the gluco-and galactopyranosides 25 and 28 and (Bu₃Sn)₂O afforded high yields of the 2,6-disulfate 26a and the 3,6-disulfate 29a , respectively. Stannylation of 25 and 28 with Bu₂SnO and sulfation proceeded less satisfactorily. Stannylation of the phenylboronate 32 (Bu₂SnO) and sulfation gave good yields of the 2-sulfate 27a ; stannylation and benzoylation yielded the 2-benzoate 34 (Scheme 2). Similarly, the galactose-derived 37 provided high yields of the 3-sulfate 30a and of the 3-benzoate 39 . Direct sulfation of the phenylboronates 32 and 37 proceeded in lower yields and gave mixtures.     

Regioselective Synthesis of Polyheterohalogenated Naphthalenes via the Benzannulation of Haloalkynes

Independent control of halide substitution at six of the seven naphthalene positions of 2‐arylnaphthalenes is achieved through the regioselective benzannulation of chloro‐, bromo‐, and iodoalkynes. The modularity of this approach is demonstrated through the preparation of 44 polyheterohalogenated naphthalene products, most of which are difficult to access through known naphthalene syntheses. The outstanding regioselectivity of the reaction is both predictable and proven unambiguously by single‐crystal X‐ray diffraction for many examples. This synthetic method enables the rapid preparation of complex aromatic systems poised for further derivatization using established cross‐coupling methods. The power and versatility of this approach makes substituted naphthalenes highly attractive building blocks for new organic materials and diversity‐oriented synthesis.