Synthesis transposition

The double bond transposition could also be achieved by the conversion of an intermediate for PGA2 synthesis into a 1,3-diene iron tricarbonyl complex from which PGC2 was synthesized in four steps. The Fe(CO)3 diene complex which survived the Wittig reaction was cleanly removed by Collins reagent in the subsequent step (Ref. 10). 

Lytic growth of Mu can occur either upon initial infection, if the c gene repressor is not formed, or by induction of a lysogen. In either case, replication of Mu DNA involves repeated transposition of Mu to multiple sites on the host genome. Initially, transcription of only the early genes of Mu occurs, but after gene C protein, a positive activator of late RNA synthesis, is expressed, the synthesis of the Mu head and tail proteins occurs. Eventually, expression of the lytic function occurs and mature phage particles are released. 

Besson and coworkers reported an original approach for the synthesis of the rare thiazolo-[5,4-/]-quinazoline 29 in six steps [15] from commercially available 2-amino-5-nitrobenzonitrile 22 (Scheme 8.11). The authors studied the transposition of four steps (ii, iii, vi, and vii) of the synthesis of thiazoloquinazoline 29 to microwave irradiation of solutions, with the same concentration of starting material and volume of solvent, and found that yields of the desired compounds were better than those obtained by conventional heating (Tab. 8.3). The overall time for the synthesis of 29 was considerably reduced and the overall yield was enhanced. 

This same concept applies to spiroannulations of six membered rings and is illustrated in a synthesis of acorenone B 155 as outlined in Scheme 547). The notion of alkylative carbonyl transposition permits the spiro enone 156 to become a logical intermediate. The standard analysis by a retro-aldol process translates the spiro ring system of acorenone B into a geminal alkylation problem as revealed by... 

Volume 75 concludes with six procedures for the preparation of valuable building blocks. The first, 6,7-DIHYDROCYCLOPENTA-l,3-DIOXIN-5(4H)-ONE, serves as an effective /3-keto vinyl cation equivalent when subjected to reductive and alkylative 1,3-carbonyl transpositions. 3-CYCLOPENTENE-l-CARBOXYLIC ACID, the second procedure in this series, is prepared via the reaction of dimethyl malonate and cis-l,4-dichloro-2-butene, followed by hydrolysis and decarboxylation. The use of tetrahaloarenes as diaryne equivalents for the potential construction of molecular belts, collars, and strips is demonstrated with the preparation of anti- and syn-l,4,5,8-TETRAHYDROANTHRACENE 1,4 5,8-DIEPOXIDES. Also of potential interest to the organic materials community is 8,8-DICYANOHEPTAFULVENE, prepared by the condensation of cycloheptatrienylium tetrafluoroborate with bromomalononitrile. The preparation of 2-PHENYL-l-PYRROLINE, an important heterocycle for the synthesis of a variety of alkaloids and pyrroloisoquinoline antidepressants, illustrates the utility of the inexpensive N-vinylpyrrolidin-2-one as an effective 3-aminopropyl carbanion equivalent. The final preparation in Volume 75, cis-4a(S), 8a(R)-PERHYDRO-6(2H)-ISOQUINOLINONES, il lustrates the conversion of quinine via oxidative degradation to meroquinene esters that are subsequently cyclized to N-acylated cis-perhydroisoquinolones and as such represent attractive building blocks now readily available in the pool of chiral substrates. 

The synthetic usefulness of dioxin vinylogous esters as p-keto vinyl cation equivalents was demonstrated by a variety of reductive and alkylative 1,3-carbonyl transpositions.5 7 Regioselective alkylation and hydroxylation at the a -position (and, in some cases, at the y-position)8 9 further extend the usefulness of 1,3-dioxin vinylogous ester templates in organic synthesis. 

The next steps of the synthesis, which formally involves a 1,2-carbonyl transposition from C(3) to C(2) and its conversion to the desired endo-N group, followed by a Mannich condensation, are outlined in Schemes 13.2.4 -13.2.6. 

The introduction of the double bond of rac-14 was performed by conversion of rac-13 into its a-phenylselenide, subsequent peroxide oxidation, and elimination. Following the synthesis reported by Mehta and Srinivas, an alkylative enone transposition was used as the last step towards irradiation... 

Ikegami s successful synthesis of racemic 720 materialized by initial conversion of 701 to 725 via a 1,2-carbonyl transposition sequence (Scheme LXXVIII) Treatment of 725 with methoxycarbene, deprotection, and oxidation provided 72 6. Acid-promoted cyclopropane ring cleavage and added functional group manipulation led to 727 which could be allylated stereoselectively. The tricyclic enone 724 was subsequently produced conventionally. 

The consecutive formation of o-hydroxybenzophenone (Figure 3) occurred by Fries transposition over phenylbenzoate. In the Fries reaction catalyzed by Lewis-type systems, aimed at the synthesis of hydroxyarylketones starting from aryl esters, the mechanism can be either (i) intermolecular, in which the benzoyl cation acylates phenylbenzoate with formation of benzoylphenylbenzoate, while the Ph-O-AfCL complex generates phenol (in this case, hydroxybenzophenone is a consecutive product of phenylbenzoate transformation), or (ii) intramolecular, in which phenylbenzoate directly transforms into hydroxybenzophenone, or (iii) again intermolecular, in which however the benzoyl cation acylates the Ph-O-AfCL complex, with formation of another complex which then decomposes to yield hydroxybenzophenone (mechanism of monomolecular deacylation-acylation). Mechanisms (i) and (iii) lead preferentially to the formation of p-hydroxybenzophenone (especially at low temperature), while mechanism (ii) to the ortho isomer. In the case of the Bronsted-type catalysis with zeolites, shape-selectivity effects may favor the formation of the para isomer with respect to the ortho one (11,12). 

One of the most versatile methodologies of EPC synthesis of allenes is the chirality transfer reaction which involves highly stereoselective, mechanism-controlled, metal-mediated propyn-yl-allenyl transpositions. Of these, the organocopper(l)-mediated reactions are especially useful and provide a relatively straightforward route to a broad variety of allenes of high enantiomeric purity. 

Thermal bond transposition has been utilized successfully in the synthesis of a number of relatively heat-insensitive families of heteroannulenes, such as the triheteronin frame (20) constructed thermally from the tetracyclic valence tautomer and the tetrabenzo heteronins (18) obtained by thermal bond transposition of their spirostructured valence tautomers (113). Similarly, thermally induced bridge extrusion (C02) has been utilized as a means of preparing dihydrobenzazonine (112) (the direct photoprogenitor of aza[13]annulene 36a) from cycloadducts (104) (73TL3805). 

A simple transposition of a C=C bond occurs during metabolism of the common fatty acid oleic acid (see Fig. 17-9), and you will encounter some spectacular examples of double-bond repositioning in the synthesis of cholesterol (see Fig. 21-35). 

Transposition of DNA, which is discussed in Chapter 27, Section D,4, may seem to be a rare and relatively unimportant event in our body cells. However, transposon DNA accounts for 35% or more of the human genome740 and apparently plays a major role in evolution. Like other transposons, the DNA sequences known as retrotransposons also move about within DNA. However, they use an indirect mechanism that involves synthesis of mRNA and reverse transcription.740 741 The reverse transcribed complementary DNA may be inserted back into the genome at new locations. The necessary chemical reactions parallel those involved in the replication of retroviruses (Fig. 28-23, 28-24). Retrotransposens, truncated retrotransposons, and related sequences constitute as much as 16% of the human genome.741... 

Allylimidates underwent a clean Claisen-type rearrangement in the presence of 5 mol % palladium chloride (equation 28),40 as did allyl carbamates39 and S-allylthioimidates (equation 29).41 This S to N rearrangement has found application particularly in the synthesis of pyrimidines, systems for which thermal S to N allylic rearrangements were generally ineffective (equation 30).42 Finally, 0-allyI S-methyl dithiocarbonates cleanly underwent palladium(ll)-catalyzed O to S allylic transposition (equation 31 ).43... 

C-H Bond activation [ 1 ] and C-C bond formation are two of the key issues in organic synthesis. In principle, the ene reaction is one of the simplest ways forC-C bond formation, which converts readily available olefins into more functionalized products with activation of an allylic C-H bond and allylic transposition of the C=C bond. The ene reaction encompasses a vast number of variants in terms of the enophile used [2]. 

This oxidative transposition of tertiary allylic alcohols into enones or enals is carried out under mild conditions and has ample application in organic synthesis. Although, it can be carried out with other chromium-based reagents (see pages 16 and 35), PCC is the reagent of choice.272... 

C-S Transposition.2 A synthesis of the cycloundecanone 5 from 2 involves reaction with 1 to give the carbinol 3. Treatment of 3 with CsF gives a product tentatively formulated as 4. The synthesis of 5 is completed by desulfuration with Raney nickel. 

A recently published full account of another synthesis [69] of the same alkaloid starting from the /rans-cinnamic ester 264 represented a different approach (ACD -> ACDB) to ( )-lycorine (Scheme 42). An intramolecular Diels-Alder reaction of 264 in o-dichlorobenzene furnished the two diastereomeric lactones 265 (86%) and 266 (5%) involving the endo and exo modes of addition respectively. The transposition of the carbonyl group of 265 to 267 was achieved by reduction with lithium aluminium hydride, followed by treatment of the resulting diol with Fetizon s reagent, which selectively oxidised the less substituted alcohol to give isomeric 5-lactone 267. On exposure to iodine in alkaline medium 267 underwent iodolactonisation to afford the iodo-hydroxy y-lactone 268. The derived tetrahydropyranyl ether... 

Umezawa and co-workers9 have reported a new synthesis of the tetracyclic lactam (19), which is a key intermediate in Torssell s synthesis of lycorine (cf. Vol. 9, p. 139) the Japanese work (Scheme 2), therefore, represents a formal synthesis of the alkaloid. The cyclohexyl isocyanate (15) (trans-diequatorial aryl and isocyanate groups) cyclized to a tricyclic lactam, which by reduction with a hydride and hydrolysis gave the ketone (18). The tetracyclic ketone (16) was converted into the 2,3-ene (17) by a Cope elimination reaction, and the synthesis of compound (19) was completed by transposition of the lactam carbonyl group from C-5 to C-7. 

The Overman Rearrangement allows the conversion of readily available allylic alcohols into allylic amines by a two-step synthesis involving the rearrangement of an allylic trichloroacetimidate to an allylic trichloroacetamide with clean 1,3-transposition of the alkenyl moiety. 

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