Allyl silyl ethers cycloadditions

Kibayashi and coworkers have used enantiometrically pure allylic silyl ethers obtained from amino acids in cycloaddition with nitrones (Eq. 8.49).71 Cyclic nitrone reacts with a chiral allyl ether to give selectively the exo and erythro isomer (de 90%). Optically active alkaloids containing a piperidine ring such as (+)-monomorine,71c (+)-coniine,71a and (-)-oncinotine71b have been prepared from the addition product. 

Very few Ni-allene complexes have been isolated and characterized, but many such species have been postulated as key intermediates in organic transformations catalyzed by Ni precursors. Notable examples of such applications include the cyclization of two arynes and one allene to give 10-methylene-9,l-dihydrophenanthrenes, " the one-pot coupling of allenes with aldehydes and silanes to give allyl silyl ethers, selective [3+2]-cyclization of allenes and Fischer carbenes, regio- and stereoselective, three-component assembly of allenes with aryl iodides and alkenyl-zirconium reagents, and regio- and chemoselective [2+2+2]-cycloaddition of electron-deficient diynes with allenes to polysubstituted benzene derivatives. ... 

The required chain extension of 12 was accomplished via deprotonation with NaH and condensation with aldehyde 7 to afford the Diels-Alder precursor 13 in 50% yield. Thermolysis of triene 13 and lactam 3 in xylene at 170 C for four days resulted in the desired cycloaddition to 14. Chromatographic purification permitted isolation of pure 14 in addition to a small amount of an exo isomer (>4 1 ratio). Acid treatment induced cleavage of both the silyl ether and acetonide. Reprotection of the diol and selective epoxidation of the A olefin produced 15 in 64% yield from 12. Epoxide 12 was then transformed to the isomeric allylic alcohol 16 by conversion of the alcohol to the bromide followed by reductive elimination. Protecting-group manipulation and subsequent oxidation the gave aldehyde 17, which was homologated and hydrolyzed to give seco acid 18 in 32% overall yield from 16. 

EtAlCb catalyzes the Friedel-Crafts acylation of alkenes with acid chlorides, the formal [3 + 2] cycloaddition of alkenes with cyclopropane-1,1-dicarboxylates (eq 21), the Friedel-Crafts alkylation of anilines and indoles with ct-aminoacrylate esters, and the formation of allyl sulfoxides from sulfinyl chlorides and alkenes. EtAlCU induces the Beckmann rearrangement of oxime sulfonates. The cationic intermediates can be trapped with enol silyl ethers (eq 22). EtAlC is the preferred catalyst for addition of the cation derived from an a-chloro sulfide to an alkene to give a cation which undergoes a Friedel-Crafts alkylation (eq 23). ... 

On the other hand, the corresponding tin precursor (63) undergoes smooth cycloaddition with a wide variety of aldehydes to produce the desired methylene-tetrahydrofnran in good yields [32, 33]. Thus prenylaldehyde reacts with (63) to give cleanly the cycloadduct (64), whereas the reaction with the silyl precursor (1) yields only decomposition products (Scheme 2.20) [31]. This smooth cycloaddition is attributed to the improved reactivity of the stannyl ether (65) towards the 7t-allyl ligand. Although the reactions of (63) with aldehydes are quite robust, the use of a tin reagent as precursor for TMM presents drawbacks such as cost, stability, toxicity, and difficult purification of products. 

ISOC reaction was employed to synthesize substituted tetrahydrofurans 172 fused to isoxazolines (Scheme 21) [44b]. The silyl nitronates 170 resulted via the nitro ethers 169 from base-mediated Michael addition of allyl alcohols 168 to nitro olefins 167. Cycloaddition of 170 followed by elimination of silanol provided 172. Reactions were conducted in stepwise and one-pot tandem fashion (see Table 16). A terminal olefinic Me substituent increased the rate of cycloaddition (Entry 3), while an internal olefinic Me substituent decreased it (Entry 4). 

Some examples of the lateral cyclization of suitable O-allyl and O-propargyl derivatives were discussed in CHEC-11(1996) <1996CHEC-II(8)747>. Thermal reaction of silyl diazoacetate 303 in xylene provides unspecific decomposition and a minor amount (about 2%) of a colorless solid can be precipitated with ether. The X-ray diffraction analysis identified the structure 305, which is a product of the lateral criss-cross cycloaddition of primarily formed azine 304 (Scheme 43) <2000T4139>. 

The ring-opening of the cyclopropane nitrosourea 233 with silver trifiate followed by stereospecific [4 + 2] cycloaddition yields 234 [129]. (Scheme 93) Oxovanadium(V) compounds, VO(OR)X2, are revealed to be Lewis acids with one-electron oxidation capability. These properties permit versatile oxidative transformations of carbonyl and organosilicon compounds as exemplified by ring-opening oxygenation of cyclic ketones [130], dehydrogenative aroma-tization of 2-eyclohexen-l-ones [131], allylic oxidation of oc,/ -unsaturated carbonyl compounds [132], decarboxylative oxidation of a-amino acids [133], oxidative desilylation of silyl enol ethers [134], allylic silanes, and benzylic silanes [135]. 

Addition of an T -allyl-Fp complex to this compound affords an T -aIlyl-Fp-substituted cycloheptatriene system. Two double bonds are involved in an (T -diene)iron complex. The remaining free double bond of the silyl enol ether attacks as a nucleophile at the cationic r -alkene-Fp moiety to form an (Tj -diene)iron complexed cyclopentane annulated cycloheptadienone. Treatment with CAN in methanol under carbon monoxide atmosphere releases the methoxycarbonyl-substituted free ligand (Scheme 4-25). Reaction of the Ti -dienyliumiron intermediate of Scheme 4-25 with an ( , Z)-isomeric mixture of ri -crotyl-Fp proceeds with high diastereoselectivity. Four new stereogenic centers are formed in the course of this formal [3+2] cycloaddition. A hetero [3+2] cycloaddition is also feasible between T -ailyl-Fp complexes and aromatic aldehydes in the presence of zinc chloride or titanium(IV) chloride to provide tetrahydrofuran derivatives (Scheme 4-26). A 1,2-shift of the iron complex fragment occurs in the course of this reaction. Employment of imines affords the corresponding pyrrolidines. ... 

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