1. 6.5 [3,3]Sigmatropic Rearrangements The principles of orbial symmetry established that concerted [3,3] sigmatropic rearrangements are allowed processes. Stereochemical predictions and analyses are based on the cyclic transition state implied by a concerted reaction mechanism. 6.5.1. Cope Rearrangements The cope rearrangement is the conversion of a 1,5-hexadiene derivatives to an isomeric 1,5-hexadiene by the [3,3] sigmatropic mechanism. When a chair transition state is favored, the E,E- and Z,Z-dienes lead to anti-3,4-diastereomers whereas the E,Z and Z.E-isomers give the 3,4-syn product.

4. Transition state B is less favorable than A because of the axial placement of the larger phenyl substituent. favorable

5. The products corresponding to boatlike transition states are usually not observed for acyclic dienes. However, the boatlike transition state is allowed, and if steric factors make a boat transition state preferable to a chair, reaction will proceed through a boat.

6. The position of the final equilibrium is governed by the relative stability of the starting material and the product. The equilibrium is favorable for product formation because the product is stabilized by conjugation of the alkene with the phenyl ring or the double bonds in the product are more highly substituted, and therefore more stable. (Scheme 6.11, entries 1 & 2) In the ring strained molecules, the Cope rearrangements can occur at much lower temperatures and with complete conversion to ring-opened products. -40 o C

9. With transition metal catalysts, such as PdCl 2 (CH 3 CN) 2 The rearrangements occurs at r.t., as contrasted to 240 o C in its absence. The electrophilic character of Pd(II) facilitates the reaction.

10. Oxy-Cope rearrangement: The formation of the carbonyl compound provides a net driving force for the reaction. The reaction is catalyzed by base. When the C-3 hydroxyl group is converted to its alkoxide the reaction is accelerated by factors of 10 10 -10 17, which is called anion Oxy-Cope rearrangements. The reactivity trend is K + >Na + >Li +.

12. Catalysis of Claisen rearrangements has been achieved using highly hindered bis(phenoxy)methylaluminum as a Lewis acid for E/Z control of the products. Very bulky catalysts tend to favor the Z-isomer by forcing the  -substituent of the allyl group into an axial conformation. Several variation of the Claisen rearrangement.

13. Scheme 6.12. Claisen Rearrangments

19. The configuration of the new chiral center is that predicted by a chairlike transition state with the methyl group occupying a pseudoequatorial position. The stereochemistry of the silyl enol ether Claisen rearrangement is controlled not only by the stereochemistry of the double bond in the allyl alcohol but also by the stereochemistry of the silyl enol ether.

20. If the enolate is prepared in pure THF, the E-enolate is generated. But if HMPA is included in the solvent, the Z-enolate predominates due to acyclic transition state. E-silyl enol ethers rearrange somewhat more slowly than the corresponding Z-isomers, This is interpreted as resulting from the pseudoaxial placement of the methyl group in the E-transition state.

21. The larger R accelerates the reaction rate, because the steric interaction with R are relieved as the C-O bond stretches. The rate acceleration would reflect the higher ground state energy resulting from these interactions.

22. The enolates of  -alkoxy esters give the Z-silyl derivatives because of chelation by the alkoxy substituent. The E-isomer gives a syn orientation whereas the Z-isomer gives rise to anti -stereochemistry.

24. O-Allyl imidate esters undergo [3,3] sigmatropic rearrangements to N-allyl amides. Yields in the reaction are sometimes improved by inclusion of K 2 CO 3 in the reaction mixture.

25. Imidates rearrangements are catalyzed by palladium salts.

26. Aryl allyl ethers can undergo [3,3] sigmatropic rearrangement. If both ortho-positions are substituted, the allyl group undergoes a second sigmatropic migration, giving the para-substituted phenol.

27. 6.6. [2,3] Sigmatropic Rearrangements The rearrangements of allylic sulfoxide, selenoxide, and nitrones are the most useful examples of the first type whereas rearrangements of carbanions of a allyl ethers are the major examples of the anionic type.

28. Phenyl thiolate to cleave S-O bond Allylic sulfonium ylides readily undergo [2,3] sigmatropic rearrangement.

29. Ring expansion sequence for generation of Medium-sized rings.

31. X = N and Y = O -

32. Anilinosulfonium ylides The Wittig rearrangement in which a strong base converts allylic ethers to  -allyl alkoxides. Because the deprotonation at the  ’carbon must cmpare with deprotonation of the  carbon in the allyl group.

33. Cyclic 5-membered ring transition state in which the  substituent prefers an equatorial orientation.

34. 6.7 Ene Reaction Certain electrophilic carbon-carbon and carbon-oxygen bonds can undergo an addition reaction with alkenes in which an allylic hydrogen is transferred to the electrophile.

37. Ene reaction have relatively high activation energies and intermolecular reaction is observed only for strongly electrophilic enophiles.

39. The thermal ene reaction of carbonyl compounds generally requires electron- attracting substituents. The reaction shows a primary kinetic isotopic effect indicative of C-H bond breaking in the rate determining step. The observations are consistent with a concerted process. The ene reaction is strongly catalyzed by Lewis acids such as aluminum chloride and diethylaluminum chloride. Coordination by the aluminum at the carbonyl group increases the electrophilicity of the conjugated system and allows reaction to occur below room temperature, as illustrated in entry 6.

40. 6.8 Unimolecular Thermal Elimination Reactions 6.8.1. Cheletropic Elimination The atom X is normally bound to other atoms in such a way that elimination will give rise to a stable molecule.

41. The stereochemistry is consistent with conservation of orbital symmetry. -

44. 6.8.2 Decomposition of Cyclic Azo Compounds X-Y = -N=N- 16 decomposes to norbornene and nitrogen only above 100 o C. But 17 eliminates nitrogen immediately on preparation, even at -78 o C. Because a C-N bond must be broken without concomitant compensation by carbon- carbon bond formation, the activation energy is much higher than for a concerted process. [2  + 2  ] forbidden (high energy) [2  + 4  ] allowed (low energy) photochemically Nonconcerted diradical mechanism

45. The stereochemistry varies from case to case.

46. Pyridazine-3,6-dicarboxylate ester react with electron-rich alkenes 1,2,4-triazine and 1,2,4,5-tetrazines Heteroaromatic ring

47. 6.8.3.  -elimination involving cyclic transition state Thermal syn elimination Amine oxide pyrolysis occurs at temperatures of 100-150 o C. The reaction can proceed at room temperature in DMSO. These reaction is thermally activated unimolecular reactions that normally do not involve acidic or basic catalysts.