Synthesis of ICs

In this section we limit our discussion to a general presentation of the alkali-metal intercalation compounds the synthesis of ICs and the geometrical factors affecting the intercalation in lamellar compounds, i.e., transition-metal dichalcogenides and transition-metal oxides are discussed. The electronic side is described in the following Chapter. 

Ternary compounds AJ 4X2 (/I = alkali metal M = transition metal X = S, Se 0 X 1) were first described by Riidorff [24] and Omloo and Jellinek [25]. Layered MX2 compounds probably represent on of the best host structure examples capable 

In a battery operation there will be repeated charging and discharging. The alkah ion insertion/extraction process of a solid-state host matrix undergoes reduction- 

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Scheme 8 Synthesis of ICs via Cadogan ring closure and double N-arylation...

Scheme 9 Synthesis of ICs from Fischer indolization reaction...

As a new and practical synthesis of pyrroles, Zard and coworkers have presented the reduction of Y-nitroketones v/ith formamidinesiilfinic acid fEq. IC.Bi/... 

Reynhout IC, Lowik D, van Hest JCM et al (2005) Solid phase synthesis of biohybrid block copolymers. Chem Commun 602-604... 

Zhao and Larock have described the synthesis of carbazoles, indoles, and dibenzofurans 118 via a Ic type cyclization that follows a sequence of Pd-catalyzed cross-coupling of alkynes and aryl iodides 116, then nitrogen-directed palladium migration to an arylpalladium intermediate 117 that undergoes an intramolecular Mizoroki-Heck ring closure <06JOC5340>. 

The synthesis of the representative compound of this series, 1,4-dihydro-l-ethyl-6-fluoro (or 6-H)-4-oxo-7-(piperazin-l-yl)thieno[2/,3/ 4,5]thieno[3,2-b]pyridine-3-carboxylic acid (81), follows the same procedure as that utilized for compound 76. Namely, the 3-thienylacrylic acid (77) reacts with thionyl chloride to form the thieno Sjthiophene -carboxyl chloride (78). Reaction of this compound with monomethyl malonate and n-butyllithium gives rise to the acetoacetate derivative (79). Transformation of compound 79 to the thieno[2 3f 4,5]thieno[3,2-b]pyhdone-3-carboxy ic acid derivative (80) proceeds in three steps in the same manner as that shown for compound 75 in Scheme 15. Complexation of compound 75 with boron trifluoride etherate, followed by reaction with piperazine and decomplexation, results in the formation of the target compound (81), as shown in Scheme 16. The 6-desfluoro derivative of 81 does not show antibacterial activity in vitro. 

Asymmetric synthesis of 2,5-dimethyl-2,4-hexadiene (28) and /-menthyl diazoacetate (29) with chiral copper complexes (30) was successfully conducted by Aratani et al. [13] to afford the (1 A)-chrysanthem ic acid /-menthyl ester (31) in high optical and chemical yield. Since this finding, a lot of chiral copper complexes have been reported and applied to the asymmetric synthesis of (IR)-chrysanthemate. However, these copper complexes required more than 1 mol% of the catalyst and the cis/trans ratio still remains unsatisfactory. Moreover, /-menthyl ester was crucial for the high enantioselectivity. Given an industrial production of... 

About the same time, and independently of this study, a group at Sandoz reported [3] the synthesis of 3-indolyltropine esters such as ICS 205-930 (8) with a pharmacological profile similar to that of MDL 72222. In this case the strategy [55] had been to select 5-HT, metoclopramide and 5-carboxami-dotryptamine (9) [56] as the starting points and carry out a systematic modification of the carboxamide group and the side-chain at C-3 on the indole nucleus. 

Following this strategy, the stereoselective synthesis of the HU stereoisomer of novel tetra-phosphonatocavitands having lower rim functionality has been reported [66, 67]. Cavitands 12c-12f were respectively synthesized from functionalized resorc[4]arenes Ic-lf. The addition of 1-decanethiol to 12f in the presence of 9-borabicyclo[3.3.1]nonane (9-BBN) in THF afforded cavitand 12g in 80 % yield (Scheme 15). 

Later Grubbs discovered ruthenium carbene complex and used it for a metathesis reaction to synthesize cyclic compounds 5a-d [Eqs. (6.4) and (6.5)]. In 1995, Grubbs found that ruthenium benzylidene carbene complex Ic," which is now commercially available, has the same reactivity as that of lb. Many researchers have therefore used this complex for olefin metathesis, and this reaction has been useful for the synthesis of carbo- and heterocyclic compounds and fused bicyclic compounds [Eq. [6.6)] °... 

The synthetic utility of this methodology was further demonstrated in a formal synthesis of (+)-biotin by the same authors [211], Following this work, various reusable immobilised analogues of (DHQD) AQN were reported to catalyze the desymmetrization of a number of meso-cyc ic anhydrides with good selectivities [212-214],... 

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