A novel aza-di-Π-methane rearrangement the photoreaction of 4,4-dimethyl-1,6,6-triphenyl-2-aza-hexa-2,5-diene

The synthesis and the novel photochemical aza-di-π-methane reaction of 4,4-dimethyl-1,6,6-triphenyl-2-aza-hexa-2,5-diene are described.     

Photochemistry of 4,4-Dialkoxy-2,5-cyclohexadienones

Irradiation (λ > 370 nm) of 4,4-dimethoxy-2,5-cyclohexadienone ( 1 a ) in benzene affords mainly the ketene acetal 4 a , which then undergoes further rearrangement. The carbomethoxycyclopentenones 6 and 7 were isolated in modest yields (10–15°). It is conceivable that the latter results from decomposition of the unobserved bicyclohexenone 5 a , the formation of which could be expected by analogy to e.g. 1 c → 5 c . Compound 4 a is presumably formed via 1,2 hydrogen shift from the intermediate zwitterion 3 a . Under similar irradiation conditions 1,4-dioxa-spiro[4.5] deca-6,9-dien-8-one ( 1 b ) gave 4 b as the only definable product. In i-C₈H₁₈ 1 a gave p-methoxyphenol ( 8 ) as the only product, most probably via hydrogen abstraction.     

Photochemical rearrangement of 5,5-diaryl-2,5-dihydrofurans

Direct irradiation of 5,5-diaryl-2,5-dihydrofurans results in a di-π-methane rearrangement to give 3-penten-1-one derivatives. Triplet sensitization leads to the formation of a 2-oxyabicyclo[2.1.0]pentane which is extremely sensitive to heat and oxygen.     

Thermal rearrangement of 2,5-diaryl-3,3,4,4-tetracyanopyrrolidines

It was shown that briefly boiling solutions of 2,5-diaryl-3,3,4,4-tetracyanopyrrolidines in DMF caused rearrangement into 5-aryl-2-(N-arylidenamino)-3,4-dicyanopyrroles, which are methylated with diazomethane both at the NH bond and at the carbon atom of the azomethine fragment.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 42–46, January, 1995.     

Reaction of 4-oxo-2,3,5,6-tetrafluorocyclohexa-2,5-dienylidene with acetylene: a carbene to carbene reaction.

The EPR spectrum of triplet 4-oxo-2,3,5,6-tetrafluorocyclohexa-2,5-dienylidene 1 was recorded in solid argon at 15 K. Carbene 1 reacts with acetylene under the conditions of matrix isolation yielding triplet vinylmethylene 4, which was characterized by its IR, UV-vis, and EPR spectrum. Carbene 4 is photolabile and is converted to spiro compound 5 on irradiation with lambda > 515 nm. The reaction of triplet carbene 1 with acetylene to produce triplet carbene 4 is predicted to be exothermic by 55 kcal mol(-1) at the B3LYP/6-31G(d,p) level of theory. The cis isomer is calculated to be only 0.4 kcal mol(-1) less stable than trans-4 at this level of theory. According to our calculations, singlet carbene S-4 is not a minimum on the C(8)F(4)H(2)O potential energy surface; however, at the T-4 geometry, the lowest lying singlet state is predicted to be 20.7 kcal mol(-1) higher in energy. The subsequent photochemical cyclization of T-4 yielding spiro compound 5 is exothermic by 10.3 kcal mol(-1) relative to T-4 and by 31.1 kcal mol(-1) relative to S-4. 4-Ethinyl-2,3,5,6-tetrafluorocyclohexa-2,5-dienone 9, the C-H insertion product of 1 and acetylene, was not observed experimentally, although it is favored energetically by 4.3 kcal mol(-1) over 5.     

Synthesis of 1,3-bis[(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)(dimethoxyphosphoryl)methyl]-4,6-dimethoxybenzene

A reaction of 1,3-dimethoxybenzene with dimethyl (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidenemethyl)phosphonate gave rise to 1,3-bis[(3,5-di-tert-butyl-4-hydroxyphenyl)-(dimethoxyphosphoryl)methyl]-4,6-dimethoxybenzene, which was oxidized to 1,3-bis[(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)(dimethoxyphosphoryl)methyl]-4,6-dimethoxy-benzene.     

Synthesis of novel phosphorus-containing sterically hindered phenols by the reaction of diphenyl (3,5-di-tert-butyl-4-oxocyclohexa-2,5-dienylidene)methylphosphonate with phenols

Diphenyl (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate was oxidized to the corresponding methylidenequinonoid derivative. The addition of phenols to the exocyclic double bond of this compound gave phosphonates with two phenol moieties.     

On the absolute stereochemistry of the photochemical rearrangement of 2,5-cyclohexadienones to lumiketones

Specification of the absolute configurations of starting material and product in the photochemical rearrangement of a 2,5-cyclohexadienone to a bicyclo[3.1.0]hexen-2-one (lumiketone) permits unambiguous determination of the stereochemistry at two crucial stages in the generally accepted reaction mechanism, namely the electrocyclic ring closure to give a 3,5-bonded intermediate, and the subsequent [1,4]-sigmatropic shift. The stereochemical course of the latter process in turn allows specification of whether the rearrangement is occurring directly from an electronically excited intermediate or a ground state zwitterion. An unconstrained monocyclic chiral cyclohexadienone has been studied in which steric constraints are minimal, and in which the system should have free choice of available pathways. The absolute configuration of the resolved dienone was determined by X-ray crystallographic analysis of a derivative containing a chiral center of known configuration. The absolute configuration of the resultant optically active diastereomeric lumiketones has been assigned from the Cotton effects observed on the corresponding dihydrolumiketones, assuming these chiroptical effects are governed by a normal Octant Rule instead of the Inverse Octant Rule which empirically correlates such data for cyclopropyl ketones lacking polarizable substituents. The limitations on these assignments are discussed, as well as alternative efforts to obtain completely unambiguous stereochemical assignments for the lumiketones. On the basis of these assignments, it is concluded that the sigmatropic shift proceeds with inversion of configuration at the migrating carbon, consistent with reaction via a ground state zwitterion.     

Transannular rearrangement of activated 2,5-diketopiperazines: a key route to original scaffolds

An efficient and original stereocontrolled transannular rearrangement starting from activated 2,5-diketopiperazines has been developed, an opportunity for the medicinal chemistry field, which requests access to novel biological scaffolds. This powerful ring contraction, which can be related to a stereoselective aza-version of the Chan rearrangement, allows for example the one-step synthesis of various tetramic acids, access to 2-disubstituted statins, or the synthesis of relevant lactam-constrained dipeptide mimetics using a TRAL-RCM sequence.     

Diterpenoid total synthesis—XXI : The synthesis of 4,4-bisnorgrayanotoxin skeleton by photochemical rearrangement of cross-conjugated cyclohexadienones

The 4,4-bisnorgrayanotoxin skeleton was synthesized from the formylated cross-conjugated cyclohexadienones (5 and 5′) by a photochemical rearrangement. The nonformylated cyclohexadienone (2) gave the spiro compound (7) and the phenols (8 and 9) on photolysis in aqueous acetic acid.