Enolate bridges

Intramolecular reactions between donor and acceptor centres in fused ring systems provide a general route to bridged polycyclic systems. The cts-decalone mesylate given below contains two d -centres adjacent to the carbonyl function and one a -centre. Treatment of this compound with base leads to reversible enolate formation, and the C-3 carbanion substitutes the mesylate on C-7 (J. Gauthier, 1967 A. Belanger, 1968). 

The synthesis of polymethines with dimethylene bridges starts with aUcychc ketones (31), ketals (32), and enamines (X = NR2), or enol ethers (X = OR) (33). They possess two activated centers, methine or methylene groups, which react with Vilsmeief s reagent to produce the corresponding dyes. 

Small and Browning agree with Schbpf and Winterhalder that thebainone methyl enolate (formed by 1 6 addition in which the oxygen bridge is ruptured and ethylenic linkages produced at C —C and C —C ) may be the primary intermediate in tWs reaction since it is hydrogenated... 

When a substituent is able to resonantly stabilize the positive charge of the ionic intermediate, there is no bromine bridging and the intermediate is an open P-bromocarbocation. These carbocations have been shown to occur in the bromination of a-methylstilbenes (ref. 9), 1 and 2, and of a variety of enol ethers (ref. 10) and acetates (ref. 11). 

AnsueP This diketo-ester has five sites for enolisation ( in 30a). Attack of these enols on the other carbonyl groups could produce ring sizes from ihree to nine but only one stable non-bridged cyclic... 

C02-Bridged bimetallic zirconocene complexes have been formed from 1 and metallocarboxylic acids [229]. Reachon of 1 with metal enolates Cp(CO)3WCHR COX (X = OEt, Me, Ph) gives Cp(CO)3WCH(R )CH(R)OZrCp2(Cl). The structure for R = H and R = Me was solved by an X-ray analysis and the chemical reactivity of these organometallic products have been studied [230]. 

A number of other types of chiral auxiliaries have been employed in enolate alkylation. Excellent results are obtained using amides of pseudoephedrine. Alkylation occurs anti to the a-oxybenzyl group.93 The reactions involve the Z-enolate and there is likely bridging between the two lithium cations, perhaps by di-(isopropyl)amine.94... 

Single stranded oligomers exhibit a completely different behavior than double strands. As shown in Fig. 6, the increase of the number n of thymine bases in the bridge between the electron donor guanine and the enol ether radical cation as electron acceptor influence the rate of the electron transfer only slightly. This can be explained by the flexibility of the single strand, which levels out the distance between donor and acceptor [13]. 

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