Carbonyl-extrusion

Diazo transfer to 1 followed by irradiation in the presence of bis-(trimethylsilyl)amide led to ring contraction with concomitant carbonyl extrusion, to give 7. Dehydration to the nitrile followed selenation then set the stage for a highly diastereoselective ytterbium-catalyzed Diels-Alder reaction, to give, after reduction and protection, the pentacyclic intermediate 2. 

Decarbonylation of Aldehydes and Acyl Halides Carbonyl-extrusion... 

Similar results were observed when polymeric precursor (39) was used. Pyridine-2,3-dicarboxylic acid was the product of the reaction between trapping agent (42) and precursor (39). This compound could be explained, as below, by carbonyl extrusion and aromatization. When 3-aza-2,4-cyclo-pentadienone was generated in the presence of trapping agent (23), compound (46) was isolated after the reaction. The reduction of (46) gave 8-coniceine. 

Internal Diels-Alder cycloaddition of the (Z) triene proceeds smoothly in the presence of BF3 Et20 to give the bicyclic ketone. The ketone is converted by epimeriza-tion, carbonyl extrusion, and homologation to the sesquiterpene ( )-a-oplopenone (Eq. 53) [99]. 

Formation of carbonyl groups which may occur when polyethylene is overheated, such as in an extrusion coating operation. Here a proper balance between extrudate temperature and exposure time to air is required. 

The synthetic procedures outlined in Section 3 provide ready access to a wide variety of benzo[7>]thiepins in which the substituents are methyl, formyl and ethoxy-carbonyl. The thermal stability of the thiepins was conveniently evaluated from the half-lives of their sulfur extrusion reactions by means of H-NMR spectroscopy. The half-lives of a series of substituted benzo[b]thiepins and naphtho[2,3-f>]thiepins thus obtained are summarized in Table 1. 

The formation of compounds 2-503 proceeds via the addition of a hydrazide 2-500 onto the central carbon of an isothiocyanate 2-499. Subsequent cyclization by attack of the hydrazide nitrogen in the formed 2-501 onto the nitrile moiety gives intermediate 2-502. A further attack of the newly formed amidine nitrogen onto the carbonyl group followed by extrusion of water affords the triazoloquinolines 2-503. 

Although the acylcobalt tetracarbonyls react with hydroxide ion under phase-transfer conditions, in the presence of alkenes and alkynes they form o-adducts rapidly via an initial interaction with the ir-electron system. Subsequent extrusion of the organometallic group as the cobalt tetracarbonyl anion leads to a,(J-unsaturated ketones (see Section 8.4). In contrast, the cobalt carbonyl catalysed reaction of phenylethyne in the presence of iodomethane forms the hydroxybut-2-enolide (5) in... 

A viable iron carbonyl-mediated reduction process converts acid chlorides and bromoalkanes into aldehydes [3, 6]. Yields are high, with the exception of nitro-benzoyl chloride, and the procedure is generally applicable for the synthesis of alkyl, aryl and a,(i-unsaturated aldehydes from the acid chlorides. The reduction proceeds via the initial formation of the acyl iron complex, followed by hydride transfer and extrusion of the aldehyde (cf. Chapter 8). 

For the synthesis of carazostatin (247), the required arylamine 708 was synthesized starting from 1-methoxycyclohexa-l, 3-diene (710) and methyl 2-decynoate (711). The key step in this route is the Diels-Alder cycloaddition of 710 and 711, followed by retro-Diels-Alder reaction with extrusion of ethylene to give 2-heptyl-6-methoxybenzoate (712). Using a three-step sequence, the methoxy-carbonyl group of compound 712 was transformed to the methyl group present in the natural product. 3-Heptyl-3-methylanisole (713) was obtained in 85% overall yield. Finally, the anisole 713 was transformed to the arylamine 708 by nitration and subsequent catalytic hydrogenation. This simple sequence provides the arylamine 708 in six steps and with 26% overall yield (597,598) (Scheme 5.66). 

Three types of photoextrusion reactions have been identified in the irradiation of aryl-substituted 1,3,2-dioxathiolane 2-oxides [5 1-1-2 4-2] cycloelimination to produce a carbonyl compound, a carbene and sulfur dioxide extrusion of sulfur dioxide accompanied by a pinacol-like rearrangement to yield an aldehyde or ketone and extrusion of sulfur trioxide to give an alkene <72JOC2589>. Sensitization and quenching experiments indicate that a singlet state is responsible for the cycloelimination reaction, whereas the rearrangement and sulfur trioxide extrusion reactions arise from a triplet state <82JCR(S)175>. 

Dialkyl-l,2,4-oxadithiolane-2-5 -oxides (160) have been synthesized from the dihydro thia-diazole (161) via nitrogen extrusion and 1,3-dipolar cycloaddition of the intermediate ylide with sulfur dioxide (Scheme 45) <90BSB265>. The formation and trapping of carbonyl oxides is described... 

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