钐试剂在有机合成中的应用

钐试剂在有机合成中的应用是近年来有机合成方法学研究中的热点之一。综述了十余年来本课题组在钐试剂应用于有机合成方面所开展的有关工作：(1)二碘化钐作为偶联剂和还原剂在有机合成中的应用;(2)金属钐直接应用于有机合成;(3)三碘化钐作为路易斯酸应用于有机合成;(4)有机钐试剂在有机合成中的应用。     

(R)-α-硫辛酸合成方法的研究进展

(R)-α-硫辛酸可用于预防和治疗糖尿病及相关并发症,也可以作为保健品使用,用途广泛,因而其高效合成方法长期以来受到广泛关注。 目前,合成(R)-α-硫辛酸的方法主要有酶和化学方法催化的不对称合成、消旋体的手性拆分以及手性底物控制的不对称合成。 本文将以此为分类标准,对目前所报道的(R)-α-硫辛酸合成方法进行总结归纳和展望。     

Microwave synthesis of zeolite membranes: A review

Significant progress has been achieved in the last years on microwave synthesis of zeolite membranes. In many cases, microwave synthesis has proven to remarkably reduce the synthesis time. In addition, microwave synthesis could also result in different membrane morphology, orientation, composition, and thus the different permeation characteristics as compared with those synthesized by conventional heating. This review attempts to summarize the obtained progress in microwave synthesis of zeolite membranes. Some topics are discussed, including: (1) case study of microwave synthesis of zeolite membranes, e.g. LTA, MFI, AFI, and other types of zeolite membranes; (2) differences between conventional and microwave synthesis; (3) formation mechanism and the so called “specific microwave effect” in the case of microwave synthesis of zeolite membranes; (4) scaling-up of zeolite membrane production by employing microwave heating. The latter three topics are mainly focused on LTA type zeolite membranes. Concluding remarks and future perspective are also suggested in the end.     

Enantioselective synthesis of 2-arylpiperidines from chiral lactams. A concise synthesis of (-)-anabasine

Cyclodehydration of achiral or racemic aryl-delta-oxoacids with (R)-phenylglycinol stereoselectively affords chiral non-racemic bicyclic lactams, from which the enantiodivergent synthesis of (R)- and (S)-2-phenylpiperidine, the diastereodivergent synthesis of cis- and trans-3-ethyl-2-phenylpiperidine, and the enantioselective synthesis of the piperidine alkaloid (-)-anabasine is reported.     

Solution phase studies towards the synthesis of triarylamine oligomers using a germanium linker on a solid support

In this letter, we describe the iterative solution phase synthesis of a triarylamine trimer as proof of concept towards the synthesis of oligomeric materials by solid-phase synthesis. Our model system utilises the stability of germanium linkers to nucleophilic conditions to develop efficient steps towards oligomer synthesis via (i) selective deprotection of tert-butyl-dimethyl-silyl ether (OTBDMS) functionality, (ii) conversion to reactive trifluoromethanesulfonate (triflate) functionality and (iii) Suzuki cross-coupling reactions.     

Sugar-assisted ligation in glycoprotein synthesis

Sugar-assisted ligation (SAL) presents an attractive strategy for the synthesis of glycopeptides, including the synthesis of cysteine-free beta-O-linked and N-linked glycopeptides. Here we extended the utility of SAL for the synthesis of alpha-O-linked glycopeptides and glycoproteins. In order to explore SAL in the context of glycoprotein synthesis, we developed a new chemical synthetic route for the alpha-O-linked glycoprotein diptericin epsilon. In the first stage of our synthesis, diptericin segment Cys(Acm)37-Gly(52) and segment Val(53)-Phe(82) were assembled by SAL through a Gly-Val ligation junction. Subsequently, after Acm deprotection, diptericin segment Cys(37)-Phe(82) was ligated to segment Asp(1)-Asn(36) by means of native chemical ligation (NCL) to give the full sequence of diptericin epsilon. In the final synthetic step, hydrogenolysis was applied to remove the thiol handle from the sugar moiety with the concomitant conversion of mutated Cys(37) into the native alanine residue. In addition, we extended the applicability of SAL to the synthesis of glycopeptides containing cysteine residues by carrying out selective desulfurization of the sulfhydryl-modified sugar moiety in the presence of acetamidomethyl (Acm) protected cysteine residues. The results presented here demonstrated for the first time that SAL could be a general and useful tool in the chemical synthesis of glycoproteins.     

A Simple Synthesis of γ-Cyclohomocitral

A simple and efficient synthesis for γ-cyclohomocitral (10), a key and versatile intermediate for the synthesis of some furanosesquiterpenes, is described. The formal total synthesis of (±) Pallenscensone (2) was accomplished.     

Amino acid building blocks for efficient Fmoc solid-phase synthesis of peptides adenylylated at serine or threonine

The first straightforward building block based (non-interassembly) synthesis of peptides containing adenylylated serine and threonine residues is described. Key features include final global acidolytic protective group removal as well as full compatibility with standard Fmoc solid-phase peptide synthesis (SPPS). The described Thr-AMP SPPS-building block has been employed in the synthesis of the Thr-adenylylated sequence of human GTPase CDC42 (Ac-SEYVP-T(AMP)-VFDNYGC-NH(2)). Further, we demonstrate proof-of-concept for the synthesis of an Ser-adenylylated peptide (Ac-GSGA-S(AMP)-AGSGC-NH(2)) from the corresponding adenylylated serine building block.     

Chemical Synthesis of Native S-Palmitoylated Membrane Proteins through Removable-Backbone-Modification-Assisted Ser/Thr Ligation

The preparation of native S-palmitoylated (S-palm) membrane proteins is one of the unsolved challenges in chemical protein synthesis. Herein, we report the first chemical synthesis of S-palm membrane proteins by removable-backbone-modification-assisted Ser/Thr ligation (RBM^GABA-assisted STL). This method involves two critical steps: 1) synthesis of S-palm peptides by a new γ-aminobutyric acid based RBM (RBM^GABA) strategy, and 2) ligation of the S-palm RBM-modified peptides to give the desired S-palm product by the STL method. The utility of the RBM^GABA-assisted STL method was demonstrated by the synthesis of rabbit S-palm sarcolipin (SLN) and S-palm matrix-2 (M2) ion channel. The synthesis of S-palm membrane proteins highlights the importance of developing non-NCL methods for chemical protein synthesis.     

Enantioselective synthesis of paraconic acids

The development of a new method for the enantioselective synthesis of disubstituted gamma-butyrolactones is reported. Based on this strategy, the total synthesis of three paraconic acids, that is (-)-roccellaric acid, (-)-nephrosteranic acid and (-)-protopraesorediosic acid, and the formal total synthesis of (-)-methylenolactocin and (-)-protolichesterinic acid is described, which are important because of their antibiotic and antitumor properties. Key steps of the synthesis are copper(I)-catalyzed asymmetric cyclopropanations of furans, highly diastereoselective Sakurai allylations, Lewis acid or Lewis base catalyzed retroaldol/lactonization cascades, and ruthenium(II)-catalyzed, intermolecular cross metathesis reactions.     

A facile method to tune zeolite L crystals with low aspect ratio

We demonstrate an alternative route to tune the morphology of zeolite L crystals using C(2)H(5)OH as the co-solvent in the synthesis gel. A low aspect ratio (0.2 to 0.4) of zeolite L crystals was obtained at lower synthesis temperature (150 °C) and shorter synthesis duration (3 days).     

Enantioselective total synthesis of (-)-acetylaranotin, a dihydrooxepine epidithiodiketopiperazine

The first total synthesis of the dihydrooxepine-containing epidithiodiketopiperazine (ETP) (-)-acetylaranotin (1) is reported. The key steps of the synthesis include an enantioselective azomethine ylide (1,3)-dipolar cycloaddition reaction to set the absolute and relative stereochemistry, a rhodium-catalyzed cycloisomerization/chloride elimination sequence to generate the dihydrooxepine moiety, and a stereoretentive diketopiperazine sulfenylation to install the epidisulfide. This synthesis provides access to (-)-1 in 18 steps from inexpensive, commercially available starting materials. We anticipate that the approach described herein will serve as a general strategy for the synthesis of additional members of the dihydrooxepine ETP family.     

不同制备方法对BiOCl材料的形貌、结构与光催化性能的影响研究

对比采用溶剂热合成、传统固相合成与溶胶-凝胶合成技术,制备了四方相BiOC1和Nd3+掺杂BiOCl光催化材料.运用X射线粉末衍射(XRD)、扫描电子显微镜(SEM)及紫外-可见吸收光谱(UV-Vis),研究了不同合成方法所制备BiOCl材料的相结构、形貌和紫外-可见光吸收性能;并以甲基橙溶液为模拟废水,研究了不同方法所制备的BiOCl材料的光催化性能.结果表明:溶剂热合成的BiOCl是由纳米片组装成粒径小于1μm微球,紫外-可见吸收边为335 nm;固相合成所得BiOCl结晶度较高,其片状颗粒粒径约为6μm,紫外-可见吸收边为430n m;溶胶-凝胶合成法制得BiOCl片状颗粒粒径约为3～4 μm,紫外-可见吸收边为430 nm.进一步地对比研究了稀土离子Nd3+掺杂前后BiOCl样品的结构、紫外-可见光吸收特性,可以发现,Nd3+掺杂后样品的相结构及形貌均无变化,但吸收边均发生不同程度的红移,以溶胶-凝胶法制得的样品效果最为明显,并具有最优的光催化性能.     

Total synthesis of (-)-strychnine

Total synthesis of (-)-strychnine is described. Notable features of our synthesis include (1) palladium-catalyzed coupling of the indole and vinyl epoxide moieties, (2) synthesis of the nine-membered cyclic amine derivative from the diol precursor in a one-pot procedure, and (3) transannular cyclization of the nine-membered cyclic amine.     

Computational modelling of the YAG synthesis

Mathematical and numerical models of the yttrium aluminium garnet (YAG) synthesis are presented in the article. The models allow the effective computer simulation of the YAG synthesis. The synthesis by sol–gel and solid-state reaction methods is considered in the article. The question concerning the reasons for the observed changes in the preparation temperature by changing synthesis method is answered. The inverse modelling problem is solved: using known experimental data (synthesis time, dimensions of reactants) the unknown input parameters of the model (diffusion and reaction rate coefficients) are calculated.     

A general strategy for the synthesis of vincamajine-related indole alkaloids: stereocontrolled total synthesis of (+)-dehydrovoachalotine, (-)-vincamajinine, and (-)-11-methoxy-17-epivincamajine as well as the related quebrachidine diol, vincamajine diol, and vincarinol

[structures: see text] The highly convergent stereocontrolled total synthesis of (-)-vincamajinine (7), (-)-11-methoxy-17-epivincamajine (9), and the oxygen-bridged (+)-dehydrovoachalotine (22) are described. Key steps in the synthesis of 7 and 9 involved the stereospecific enolate-driven palladium-catalyzed cross-coupling reaction, a Tollens reaction, an acid-assisted intramolecular cyclization to form the C(7)-C(17) quaternary center, and two stereospecific reductions. The efficiency of this strategy is illustrated by the completion of the synthesis of 7 and 9 in 16 [from d-(+)-tryptophan methyl ester 17] and 17 (from the Sch?llkopf chiral auxiliary 27) reaction vessels, respectively. This constitutes the first total synthesis of these indole alkaloids and provides the first regiospecific route to 11-methoxy-substituted ajmaline/vincamajine-related alkaloids. The synthesis of 22 required a novel DDQ-mediated cyclization to furnish the C(6)-O(17) bond, executed in stereospecific fashion. Completion of these syntheses illustrates a concise and versatile strategy for the synthesis of vincamajine-related alkaloids, which has also been employed to prepare the related compounds quebrachidine diol (53), vincamajine diol (56), and vincarinol (59).     

Diversity-oriented synthesis and solid-phase organic synthesis under controlled microwave heating

Diversity-oriented organic synthesis (DOS) and solid-phase organic synthesis (SPOS) are proven technologies for generating small molecule libraries for chemical genetics studies. Integration of controlled microwave heating with DOS and SPOS not only speeds up the library preparation process but also offers unique opportunities in tackling issues which are hardly addressed by thermal heating. Microwave-assisted synthesis is illustrated for (a) highly regioselective Wittig olefination of cycloalkanones by accurate regulation of temperature; (b) tandem Wittig-IMDA sequence toward stereochemical diversity of gamma-butyrolactones; (c) one-pot alkylation-amidation approach toward appendage diversity through use of building blocks; and (d) one-pot U-4CR-annulation strategy toward skeletal diversity via careful reaction design. Microwave-assisted solid-phase organic synthesis (MASPOS) is highlighted by incorporating with split-pool combinatorial synthesis (SPCS) of indole sulfonamides via a key on-resin Cu(II)- or Pd(II)-catalyzed heteroannulation under microwave heating. Design and fabrication of a novel diglycine-derived catlinker are described and its role in facilitating on-resin reaction is evaluated. A traceless synthesis of indole sulfonamides via microwave-assisted Cu(II)-catalyzed heteroannulation of the catlinker-tethered substrates is also given.     

Evolution of a total synthesis of (-)-kendomycin exploiting a Petasis-Ferrier rearrangement/ring-closing olefin metathesis strategy

A convergent stereocontrolled total synthesis of (-)-kendomycin (1) has been achieved. The synthesis proceeds with a longest linear sequence of 21 steps, beginning with commercially available 2,4-dimethoxy-3-methylbenzaldehyde (12). Highlights of the synthesis include an effective Petasis-Ferrier union/rearrangement tactic to construct the sterically encumbered tetrahydropyran ring, a ring-closing metathesis to generate the C(4a-13-20a) macrocycle, an effective epoxidation/deoxygenation sequence to isomerize the C(13,14) olefin, and a biomimetic quinone-methide-lactol assembly to complete the synthesis.     

Total synthesis of (+)-phorboxazole A exploiting the Petasis-Ferrier rearrangement.

A highly convergent, stereocontrolled total synthesis of the potent antiproliferative agent (+)-phorboxazole A (1) has been achieved. Highlights of the synthesis include: modified Petasis-Ferrier rearrangements for assembly of both the C(11-15) and C(22-26) cis-tetrahydropyran rings; extension of the Julia olefination to the synthesis of enol ethers; the design, synthesis, and application of a novel bifunctional oxazole linchpin; and Stille coupling of a C(28) trimethyl stannane with a C(29) oxazole triflate. The longest linear sequence leading to (+)-phorboxazole A (1) was 27 steps, with an overall yield of 3%.     

Synthesis of the C(1)-C(25) fragment of amphidinol 3: application of the double-allylboration reaction for synthesis of 1,5-diols

[structure: see text] A synthesis of the C(1)-C(25) fragment of amphidinol 3 is described. The synthesis features two applications of double allylboration reaction methodology for the highly stereoselective synthesis of 1,5-diol units in the C(1)-C(15) segment.