Convergent approach, synthesis

A cursory inspection of key intermediate 8 (see Scheme 1) reveals that it possesses both vicinal and remote stereochemical relationships. To cope with the stereochemical challenge posed by this intermediate and to enhance overall efficiency, a convergent approach featuring the union of optically active intermediates 18 and 19 was adopted. Scheme 5a illustrates the synthesis of intermediate 18. Thus, oxidative cleavage of the trisubstituted olefin of (/ )-citronellic acid benzyl ester (28) with ozone, followed by oxidative workup with Jones reagent, affords a carboxylic acid which can be oxidatively decarboxylated to 29 with lead tetraacetate and copper(n) acetate. Saponification of the benzyl ester in 29 with potassium hydroxide provides an unsaturated carboxylic acid which undergoes smooth conversion to trans iodolactone 30 on treatment with iodine in acetonitrile at -15 °C (89% yield from 29).24 The diastereoselectivity of the thermodynamically controlled iodolacto-nization reaction is approximately 20 1 in favor of the more stable trans iodolactone 30. 

A dendrimer-based approach for the design of globular protein mimics using glutamic (Glu) and aspartic (Asp) acids as building blocks has been developed [151]. The preassembled Glu/Asp dendrones were attached to a 1,3-bifunctional adamantyl based on a convergent dendrimer synthesis strategy (see Fig. 28). 

Scheme 15. Rapid convergent approach of the synthesis of first-generation ruthenium-acety-...

The synthesis of both haliclamines A (64) and B (65) has been achieved (Scheme 6). The first synthesis of both 64 and 65 [35,36] was a convergent approach starting from the monoprotection and functional group interconversions (FGls) of 1,4-butanediol (66) to the monoprotected iodide (67), which... 

Frdchet et al. reported the synthesis of a unimolecular micelle (Fig. 6) generated by a convergent approach starting with 3,5-dihydroxybenzyl alcohol, as the key branched monomer unit [65]. Fourth generation dendrimer 15 with 32 carboxylic acid moieties on the periphery was synthesized and its correspond-... 

The subsequent deprotection of the hemiacetal concluded the synthesis of 1. We also successfully used this convergent approach to synthesize nakiterpiosinone (2) and 6,20,25-< /E-nakiterpiosiii (49). 

H. Ihre, A. Hult, J. M. J. Frechet, and I. Gitsov, Double-stage convergent approach for the synthesis of functionalized dendritic aliphatic polyesters based on 2,2-bis(hydroxymethyl)propionic acid, Macromolecules, 31 (1998) 4061 1068. 

The first total synthesis of (-)-reserpine (109) was published in 1956 and 1958 by Woodward and co-workers (233, 234). Although this ingenious work has already been reviewed in The Alkaloids (3), it is worthwhile to present the reaction sequence to recapitulate this convergent approach. 

The convergent approach to dendrimer synthesis has evolved considerably over the past dozen years. With the benefit of hindsight, it is clear that the key criteria for a successful convergent synthesis include ... 

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