Enantioselective crossed intramolecular [2+2] photocycloaddition reactions mediated by a chiral chelating Lewis acid

In intramolecular [2+2] photocycloaddition reactions, the two tethered olefins can approach each other in a straight or in a crossed fashion. Despite the fact that the latter reaction mode leads to intriguing, otherwise inaccessible bridged skeletons, there has so far not been any enantioselective variants thereof. This study concerned the crossed [2+2]-photocycloaddition of 2-(alkenyloxy)cyclohex-2-enones to bridged cyclobutanes. It was found that the reaction could be performed with high enantioselectivity (80–94% ee) under visible light conditions when employing a chiral rhodium Lewis acid as a catalyst (2 mol%).

An enantioselective crossed [2+2] photocycloaddition is presented which proceeds under visible light irradiation in the presence of a chiral Lewis acidic metal complex. Chelation of two oxygen atoms to the metal centre accounts for the observed enantioface differentiation.     

Solvent-controlled intramolecular [2 + 2] photocycloadditions of alpha-substituted enones

The regio- and stereoselectivity of intramolecular [2 + 2] photocycloadditions of 2'-hydroxyenones are shown to be solvent-dependent. In the presence of aprotic solvents, 2'-hydroxyenones undergo photocycloadditions in a manner consistent with the presence of an intramolecular hydrogen bond between the carbonyl group and the tether's hydroxy functionality. In protic solvents, intermolecular interactions appear to disrupt the intramolecular hydrogen bond, providing products with complementary diastereoselectivity. If the facial accessibility of the alpha-tethered olefin is limited, the cycloadditions proceed to give head-to-tail or head-to-head regioisomers, depending on the nature of the solvent employed.     

Intramolecular pyridone/enyne photocycloaddition: partitioning of the [4 + 4] and [2 + 2] pathways

Intramolecular photocycloaddition (>290 nm) between a 1,3-enyne and a 2-pyridone is far more selective than the intermolecular version; a three-atom linkage both controls regiochemistry and separates the [2 + 2] and [4 + 4] pathways. All four head-to-head, head-to-tail, tail-to-head, and tail-to-tail tetherings have been investigated. Linkage via the ene of the enyne leads to [2 + 2] products regardless of alkene geometry, whereas linkage through the yne results in [4 + 4] cycloadducts. The bridged 1,2,5-cyclooctatriene products of [4 + 4] cycloaddition are unstable and undergo a subsequent [2 + 2] dimerization reaction.     

Diastereoselective transannular [2+2] photocycloaddition of ascorbic acid derivatives

Ring-closing metathesis of bis-O,O-alkenyl ascorbic acid derivatives affords cyclic ethers in good yields which can be further converted by irradiation at 254 nm into new polyoxacyclic structures according to a diastereoselective transannular [2+2] photocycloaddition.     

Pressure effects in a [2+2] photocycloaddition and -reversion

Evidence is presented to support the conclusion that the [2+2] photocycloaddition of acrylonitrile to naphthalene has a late transition state similar in volume to those in concerted thermal cycloadditions.     

Molecular driving forces for Z/E isomerization mediated by heteroatoms: the example hemithioindigo

A combined experimental and theoretical investigation of photoinduced Z/E isomerizations is presented. Unsubstituted Hemithioindigo is selected as a representative minimal model to unravel the reaction mechanism in the presence of heteroatoms on an atomic level. Time-resolved spectroscopy reveals multiexponential reaction dynamics on the few picoseconds time scale, which are interpreted by quantum chemical calculations at the CASSCF/CASPT2 level of theory. Detailed insight into the processes governing the ultrafast decay from the first excited state, mediated by a number of conical intersections, is provided. Charge separation and charge balance recovery on the reaction pathway play the leading role and are controlled by the electron-donating or -withdrawing character of the heteroatoms. The electronic and geometric structures of the individual minimum energy conical intersections governing the reaction are rationalized, and an extended energetically low lying conical intersection seam is extracted. Comparison to the experimental results permits linking the observed time constants to molecular intermediates and pathways. An explanation is provided for the pronounced differences of Z → E and the E → Z photoreactions upon excitation to the first excited singlet state.     

[6+6]-benzo/benzo - photocycloaddition reactions

Cyclobutane-formation between “face-to-race” oriented benzenoid chromophoric units has been observed in 1,6-diene- (B) (1b–d/4a–d), not, however, in 1,5-diene-derived (C) (7a–c) skeletons.     

Investigating the arenyl-diene double [3 + 2] photocycloaddition reaction

The double [3 + 2] photocycloaddition reaction involving arenyl-dienes has been used to assemble seven separate [5.5.5.5] fenestrane structures that include ether and aza variants. The primary photolysis step was a meta photocycloaddition reaction, while a secondary photocycloaddition step formed the fenestrane structure. Investigations involving the insertion of an additional methylene group into the basic arenyl-diene skeleton failed to afford the desired [5.5.5.6] fenestrane structure. The presence of an oxime moiety in the aromatic photosubstrate allowed the primary photolysis step to take place; however, an attempted secondary photocycloaddition reaction involving the oxime did not provide the intended polyheterocyclic fenestrane. An alternative strategy to form various "criss-cross" double meta photocycloadducts was investigated and led to the discovery of a Paterno-Büchi cycloaddition reaction between acetone and an angular meta photocycloadduct. Other novel thermally and photochemically mediated skeletal rearrangement reactions were also recorded.     

Photoinduced E to Z isomerization of tetraphenylethylene derivatives within organometallic supramolecular assemblies

Isolation of E-1,2-bis(4-bromophenyl)-1,2-diphenyl-ethylene from the E/Z isomer mixture obtained by a Mc Murry coupling reaction and reaction of this isomer with imidazole followed by N-alkylation with n Bu Br and anion exchange yielded the bisimidazolium tetraphenylethylene (TPE) derivative H_2-E-1(PF_6)_2.The reaction of H_2-E-1(PF_6)_2 with Ag_2O yielded the dinuclear metallarectangle[Ag_2(E-1)_2](PF_6)_2 where the two bis-NHC donors E-1 bridge two silver atoms.Irradiation of[Ag_2(E-1)_2](PF_6)_2 leads to E/Z isomerization of the di-NHC ligand and formation of Z-1 in the mononuclear complex[Ag(Z-1)]PF_6.Demetallation of the di-NHC ligand with NH_4Cl/NH_4PF_6 yielded bisimidazolium salt H_2-Z-1(PF_6)_2.The unique isomerization of the E-TPE derivative into its Z-isomer via metal complex formation/irradiation/demetallation cannot be achieved by irradiation of the individual imidazolium salt.The emissive properties of the TPE complexes[Ag_2(E-1)_2](PF_6)_2 and[Ag(Z-1)]PF_6 have been investigated.     

Mechanisms of acid-catalyzed Z/E isomerization of imines.

The kinetics and mechanism of acid-catalyzed Z/E isomerization of O-methylbenzohydroximoyl chloride (1Za and 1Ea), methyl O-methylbenzohydroximate (1Zb and 1Eb), ethyl O-methylbenzohydroximate (1Zc and 1Ec and five para and meta substituted derivatives), O-methylcinnamohydroximoyl chloride (2Za and 2Ea), and methyl O-methylcinnamohydroximate (2Zb and 2Zb) have been investigated. The kinetics of Z/E isomerization of these imines have been studied in glacial acetic acid (1Ea and 1Zc) and in dioxane solutions containing HCl, trifluoromethanesulfonic acid, or tetrafluoroboric acid (1Ea, 1Zb, 2Ea, and 2Zb). The isomerization takes place by either (a) rotation about the carbon-nitrogen double bond of the protonated imine (iminium ion rotation) or (b) nucleophilic attack on the protonated imine to form a tetrahedral intermediate that undergoes stereomutation and loss of the nucleophile (nucleophilic catalysis). The hydroximoyl chlorides 1Eaand 2Ea only isomerize by the nucleophilic catalysis mechanism. The hydroximate 1Zb appears to be capable of isomerizing by either mechanism. The hydroximate 2Zb may be isomerizing only by iminium ion rotation. Theoretical calculations support the notion that increased conjugation in the protonated imine increases the rate of iminium ion rotation.     

Diastereoselective [2+2] photocycloaddition of polymer-supported cyclic chiral enone with ethylene

The phenylmenthyl derivative, previously shown to be very effective chiral auxiliaries in the diastereoselective [2+2] photocycloaddition of cyclic enones with the simplest olefin, ethylene, was attached to poly(ethylene glycol)-grafted Wang resin. We then investigated the diastereoselective [2+2] photocycloaddition on solid support in several solvents. As the result, we accomplished good selectivity in toluene as well as the recycle of the polymer-supported chiral auxiliary. This is the first example that bicyclo[4.2.0]octane derivative has been obtained photochemically on the solid support.     

NMR analyses of two isomeric cyclobutanes from a [2 + 2] photocycloaddition

Complete ¹H and ¹³C NMR assignments are reported for two isomeric cyclobutanes generated from the photochemical [2 + 2] cycloaddition of N‐methylisocarbostyril and 4‐methoxy‐3‐buten‐2‐one. The reaction is 100% regioselective and demonstrates the potential synthetic utility of de Mayo type reactions using an isocarbostyril and a stable β‐dicarbonyl enol derivative. Copyright © 2002 John Wiley & Sons, Ltd.     

Diastereoselective [2 + 2] photocycloaddition of stilbene to chiral fumarate. Direct versus charge-transfer excitation

The selective excitation of the charge-transfer (CT) complex and the direct excitation of the substrate gave distinctly different product ratios and diastereomeric excesses (de's), as well as their temperature dependencies, in [2 + 2] photocycloaddition of (E)-stilbene to bis((R)-1-methylpropyl) fumarate, clearly demonstrating that the excited CT complex and the conventional exciplex differ in structure and reactivity. This conclusion is supported by the contrasting fluorescence behavior exhibited by the relevant excited species, particularly at low temperatures.     

Biradical intermediate in the [2 + 2] photocycloaddition of dienes and alkenes to [60]fullerene

The photocycloaddition of vinylcyclopropanes to C60 yields stereospecifically a five-membered [60]fullerene adduct. These results suggest a biradical intermediate of the [2 + 2] photocycloaddition between dienes or arylalkenes and C60. An electron transfer between the triplet excited state of C60 and the unsaturated substrates precedes the formation of the intermediate.     

Photochemistry of benzotriazole: an unprecedented tautomer-selective intermolecular [2+2] photocycloaddition

[reaction: see text]. Irradiation of benzotriazole with a variety of maleimide derivatives leads to the stereo- and regioselective formation of aryl [2 + 2] photocycloaddition products. Further studies with 2-alkyl benzotriazole derivatives indicates that in the case of the parent benzotriazole this cycloaddition proceeds selectively via the 2H-tautomer.