Cyclobutenes results

Diene generation followed by a Diels-Alder reaction can be carried out as a one-pot reaction. Methyl 9-(3-cyclopropylcyclobut-2-enyl)nonanoate was heated with dimethyl acetylenedicarboxylate, ring opening of the cyclobutene resulted followed by cyclohexene formation due to dienophile trapping of the buta-1,3-diene intermediate giving methyl 9-[5-cyclo-propyl-2,3-bis(methoxycarbonyl)phenyl]nonanoate after oxidation. ... 

The reaction of 6-oxo-2,5-diphenyl-6/f-l,3,4-oxadiazine with cyclobutene results in the loss of nitrogen and formation of an eight-membered ring lactone <85CB2940>. Similarly, 5,6-dihydro-2-(triphenylphosphoranylideneamino)-4/f-pyran-3-carbonitrile reacts with various alkynes to give 7,8-dihydro-6/f-oxocines <86CB3515>. 

Electi ocyclic reactions are examples of cases where ic-electiDn bonds transform to sigma ones [32,49,55]. A prototype is the cyclization of butadiene to cyclobutene (Fig. 8, lower panel). In this four electron system, phase inversion occurs if no new nodes are fomred along the reaction coordinate. Therefore, when the ring closure is disrotatory, the system is Hiickel type, and the reaction a phase-inverting one. If, however, the motion is conrotatory, a new node is formed along the reaction coordinate just as in the HCl + H system. The reaction is now Mdbius type, and phase preserving. This result, which is in line with the Woodward-Hoffmann rules and with Zimmerman s Mdbius-Huckel model [20], was obtained without consideration of nuclear symmetry. This conclusion was previously reached by Goddard [22,39]. 

Such reductive ring contractions of sulfones are formally similar to two other methods capable of supplanting a sulfur atom by a carbon-carbon double bond the Ramberg-Backlundand Stevens rearrangements. The distinguishing feature of this novel approach to cyclobutenes consists in the resultant higher level of alkyl substitution at the sp -hybridized centers. 

The cyclobutene-butadiene interconversion can serve as an example of the reasoning employed in construction of an orbital correlation diagram. For this reaction, the four n orbitals of butadiene are converted smoothly into the two n and two a orbitals of the ground state of cyclobutene. The analysis is done as shown in Fig. 11.3. The n orbitals of butadiene are ip2, 3, and ij/. For cyclobutene, the four orbitals are a, iz, a, and n. Each of the orbitals is classified with respect to the symmetiy elements that are maintained in the course of the transformation. The relevant symmetry features depend on the structure of the reacting system. The most common elements of symmetiy to be considered are planes of symmetiy and rotation axes. An orbital is classified as symmetric (5) if it is unchanged by reflection in a plane of symmetiy or by rotation about an axis of symmetiy. If the orbital changes sign (phase) at each lobe as a result of the symmetry operation, it is called antisymmetric (A). Proper MOs must be either symmetric or antisymmetric. If an orbital is not sufficiently symmetric to be either S or A, it must be adapted by eombination with other orbitals to meet this requirement. 

The best way to understand how orbital symmetry affects pericyclic reactions is to look at some examples. Let s look first at a group of polyene rearrangements called electrocyclic reactions. An electrocyclic reaction is a pericyclic process that involves the cycli/ation of a conjugated polyene. One 7r bond is broken, the other 7t bonds change position, a new cr bond is formed, and a cyclic compound results. For example, a conjugated triene can be converted into a cyclohexa-diene, and a conjugated diene can be converted into a cyclobutene. 

Although the orbital-symmetry rules predict the stereochemical results in almost all cases, it is necessary to recall (p. 1070) that they only say what is allowed and what is forbidden, but the fact that a reaction is allowed does not necessarily mean that the reaction takes place, and if an allowed reaction does take place, it does not necessarily follow that a concerted pathway is involved, since other pathways of lower energy may be available.Furthermore, a forbidden reaction might still be made to go, if a method of achieving its high activation energy can be found. This was, in fact, done for the cyclobutene butadiene interconversion (cis-3,4-dichloro-cyclobutene gave the forbidden cis.cis- and rran.y, ra i -l,4-dichloro-1,3-butadienes,... 

The interaction of butadiynediyl dimetal complexes [Fp -C -CsC-M, Fp =FeCp (CO)2, M= Fp, Rp, SiMea, Rp= RuCp(CO)2] with diiron nonacarbonyl, Fe2(CO)9, results in the formation of a mixture of products, as is also observed in the case of their interaction with organic acetylenes. Interesting polymetallic complexes, propargylidene-ketene compounds, zwitterionic cluster compounds, and pa-p -propargylidene-cyclobutene compoimds were isolated from the reaction mixtures and successfully characterized. The product distributions were found to be dependent on the metal fragment (M) at the other end of the C4 rod. The results of the reaction are described... 

Subsequently, Kametani and coworkers observed a similar allylic sulfoxide-sulfenate-sulfoxide rearrangement. These authors reported the exceptionally facile ringopening reaction of condensed cyclobutenes facilitated by arylsulfinyl carbanion substituents. For example, treatment of sulfoxide 68 with butyllithium in tetrahydrofuran at — 30°C for 10 min, followed by normal workup, results in the formation of product 71, which can be explained by the intervention of a double [2,3]-sigmatropic rearrangement of the initial product 69 via 70 (equation 32). A similar double [2,3]-sigmatropic rearrangement of 1,4-pentadienylic sulfoxides has also been reported by Sammes and coworkers. ... 

Table 13-1. Computed reaction barriers and isomer stabilities [kcal/mol] for the electrocyclic ring opening of cyclobutene (relative to cyclobutene 1, including zero-point vibrational contributions). Except for G2, the results were obtained using the 6-311+G(d,p) basis set.

Excitation to produce a diradical-like intermediate (excited state) can result in either hydrogen abstraction or rearrangement and closure to form the cyclobutene ... 

This time it is conrotatory movement that results in a bonding situation, and formation of the trans dimethylcyclobutene (18). For the photochemical interconversion (which tends to lie over in favour of the cyclobutene), irradiation of the diene will result in the promotion of an electron into the orbital of next higher energy level, i.e. 3, and the HOMO to be considered now therefore becomes i/r3 (23) ... 

Intermolecular PKRs proceed especially easily with strained alkenes, e.g., nor-bornene, norbomadiene, and cyclobutene [97]. Nevertheless, highly strained MCP gave unsatisfactory results when reacted at 20 °C in hexane with acetylene, propyne, or phenylacetylene, both in terms of yields (10-15%) and of regioselec-tivity of the attack to the ethylenic bond (ca. 1 1) [100a, 103]. The reagents were consumed, but extensive tar formed and no variation in reaction conditions was successful. 

The oxidation of 2,2-dichloro-3-cyclobuten-l-ones 241 with VO(OR)Cl2 results in the regioselective formation of alkyl 2,4,4-trichloro-3-butenoates 242 with chlorination at the a-position of 243 [140]. (Scheme 97)... 

The reaction mechanism was considered to be oxidative cyclization, and pal-ladacyclopentene 32 was formed. Reductive elimination then occurs to give cyclobutene 33, whose bond isomerization occurs to give diene 28. The insertion of alkyne (DMAD) into the carbon palladium bond of 32 followed by reductive elimination occurs to give [2+2+2] cocyclization product 27. Although the results of the reactions of E- and Z-isomers of 29 with palladium catalyst 26a were accommodated by this pathway, Trost considered the possibility of migration of substituents. Therefore, 13C-labeled substrate 25 13C was used for this reaction. 

If the alkenes and acetylenes that are subjected to the reaction mediated by 1 have a leaving group at an appropriate position, as already described in Eq. 9.16, the resulting titanacycles undergo an elimination (path A) as shown in Eq. 9.58 [36], As the resulting vinyltitaniums can be trapped by electrophiles such as aldehydes, this reaction can be viewed as an alternative to stoichiometric metallo-ene reactions via allylic lithium, magnesium, or zinc complexes (path B). Preparations of optically active N-heterocycles [103], which enabled the synthesis of (—)-a-kainic acid (Eq. 9.59) [104,105], of cross-conjugated trienes useful for the diene-transmissive Diels—Alder reaction [106], and of exocyclic bis(allene)s and cyclobutene derivatives [107] have all been reported based on this method. 

A similar result was reported by Vandewalle 15°-151>. Irradiation of 1,2-bis(tn-methylsiloxy)cyclobutene and compounds (441) afforded compounds (442), which were reduced with LiAlH4 to give the endo alcohol (443). Treatment of the alcohol (443) with methanol for 24 hours would bring about silylether cleavage as well as unexpected direct oxidation of (443) to the cis-hydrindanes (444) in 50-70 % yield (Table 18)130). 

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