Ring strain presence

Intramolecular cycloadditions of substrates with a cleavable tether have also been realized. Thus esters (37a-37d) provided the structurally interesting tricyclic lactones (38-43). It is interesting to note that the cyclododecenyl system (w = 7) proceeded at room temperature whereas all others required refluxing dioxane. In each case, the stereoselectivity with respect to the tether was excellent. As expected, the cyclohexenyl (n=l) and cycloheptenyl (n = 2) gave the syn adducts (38) and (39) almost exclusively. On the other hand, the cyclooctenyl (n = 3) and cyclododecenyl (n = 7) systems favored the anti adducts (41) and (42) instead. The formation of the endocyclic isomer (39, n=l) in the cyclohexenyl case can be explained by the isomerization of the initial adduct (44), which can not cyclize due to ring-strain, to the other 7t-allyl-Pd intermediate (45) which then ring-closes to (39) (Scheme 2.13) [20]. While the yields may not be spectacular, it is still remarkable that these reactions proceeded as well as they did since the substrates do contain another allylic ester moiety which is known to undergo ionization in the presence of the same palladium catalyst. 

Oxetanes are significantly less reactive with nucleophiles due to diminished ring strain. Under certain conditions, however, amines can open oxetanes to give amino alcohols. tert-Butylamine reacts with oxetanes in the presence of Yb(OTf)3 to give 3-hydroxy amines. Lithium tetrafluorohorate has also been used for this... 

Generally, cyclohexyne is an unstable molecule because of its ring strain. However, it can be stabilized by coordination to transition metals.35 The reduction of 1,2-dibromocyclohexene by sodium/mercury in the presence of a nickel-bromide complex afforded the Ni-alkyne complex 66 as a thermally stable and isolable compound (Scheme 22).36 Complex 66 smoothly reacted with C02 under atmospheric pressure to give nickelacycle 67 in good yield. Dimethyl acetylenedicarboxylate was inserted into the vinyl-nickel bond in 67 to give the seven-membered oxanickelacycle 68. 

As discussed above, many cyclopropylamines are good inhibitors of MAOs. In addition, as discussed in Section 3.2, fluorine substitution had substantial effects on the inhibition of MAOs by such analogues as allylamines. We undertook a broadly based study of the effects of fluorine substituted on the cyclopropyl ring of cyclopropyl amines on potency and selectivity of amine oxidase inhibition. In addition to effects on amine pKg and lipophilicity, we expected additional consequences resulting from altered geometry and ring strain due to the presence of fluorine. 

The transition state of singlet carbene cycloaddition to alkenes involves an electrophilic approach of the vacant p orbital to the n bond of alkenes. By contrast, the first step of the triplet addition process may involve the in-plane a orbital of the carbene. As in the case of C—H insertion (see Section 5.1), the difference in the transition structure between the singlet and triplet cycloaddition becomes important in the intramolecular process, especially when approach to a double bond is restricted by ring strain. Direct photolysis of ( )-2-(2-butenyl)phenyldiazomethane (99) in the presence of methanol gives l-ethenyl-l,la,6,6fl-tetrahydrocycloprop [fljindene [100, 29%, (E/Z)= 10 1] and l-(2-butenyl)-2-(methoxymethyl)benzene (101, 67%). Triplet-sensitized photolysis results in a marked increase in the indene (52%, EjZ) = 1.3.T) at the expense of the ether formation (4%) (Scheme 9.30). On the other hand, direct photolysis of phenyldiazomethane in an equimolar mixture of... 

Polycycloolefins are prepared by ring opening metathesis polymerization (ROMP) using transition metal catalysts [31], By far the most commonly studied monomer is dicyclopenta-diene (Fig. 1.7). Cycloolefins with high ring strains like norbomenes and their analogs polymerize very fast and the polymerizations are quite exothermic. Metathesis catalyst systems tend to be sensitive to the presence of polar compounds and the polymerization rates... 

In the case of some cyclics, such as the thionylphosphazene six-membered ring [NS(0)Cl(NPCl2)2], the small degree of ring-strain makes the favourable A/Zrop and unfavourable TAArop terms finely balanced. In the presence of a catalyst such as GaCls, ROP can be favoured at high concentrations and depolymerisation to the cyclic monomer at low concentrations [eqn (8.2)]. 

The most striking chemical property of lipoic acid is the presence of ring strain of 17-25 kj mol 1 in the cyclic disulfide. Because of this, thiol groups and cyanide ions react readily with oxidized lipoic acid to give mixed disulfides (Eq. 15-32a) and isothiocyanates (Eq. 15-32b), respectively. 

Another result of the ring strain is that the reduction potential E° (pH 7, 25°C), is -0.30 V, almost the same as that of reduced NAD (-0.32V). Thus, reoxidation of reduced lipoic acid amide by NAD+ is thermodynamically feasible. Yet another property attributed to the ring strain in lipoic acid is the presence of an absorption maximum at 333 nm. 

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