Zwitterionic precursors

The geometry of the zwitterions with its exocylic out-of-plane methylene group was quasi-preserved in the recently reported dibenzodioxocine derivative (18) that was formed in rather small amounts by rapidly degrading the NMMO complex at elevated temperatures.45 Strictly speaking, dibenzodioxocine dimer 18 is actually not a dimer of ortho-quinone methide 3, but of its zwitterionic precursor or rotamer 3a (Fig. 6.17). As soon as the out-of-plane methylene group in this intermediate rotates into the ring plane, the o-QM 3 is formed irreversibly and the spiro dimer 9 results... 

It was shown that complexes 19 of the zwitterionic precursors of ortho-quinone methides and a bis(sulfonium ylide) derived from 2,5-di hydroxyl 1,4 benzoquinone46 were even more stable than those with amine N-oxides. The bis(sulfonium ylide) complexes were formed in a strict 2 1 ratio (o-QM/ylide) and were unaltered at —78 °C for 10 h and stable at room temperature under inert conditions for as long as 15—30 min (Fig. 6.18).47 The o-QM precursor was produced from a-tocopherol (1), its truncated model compound (la), or a respective ortho-methylphenol in general by Ag20 oxidation in a solution containing 0.50-0.55 equivalents of bis(sulfonium ylide) at —78 °C. Although the species interacting with the ylide was actually the zwitterionic oxidation intermediate 3a and not the o-QM itself, the term stabilized o-QM was introduced for the complexes, since these reacted similar to the o-QMs themselves but in a well defined way without dimerization reactions. 

Adducts of /-butyllithium to [2-(ATV-dimcthylaminometbyl)phenylJ-alkyloxymethylvinylsilanc <20020M2017> or [2-(.V,.V-dimcthylaminomcthyl)phenyl]-mcthylvinylchlorosilane lead to 1,3-disilacyclobutanes via a charge-separated zwitterionic precursor (Scheme 32) <2001BKC593>. 

El Hankari, S., Motos-Perez, B., Hesemann, P., Bouhaouss, A., and Moreau, J.J.E. (2011) Periodic mesoporous organosihca from zwitterionic precursors. Chem. Commurt, 47, 6704-6706. 

Careful re-investigation of the photolysis products of 3,5-dimethyl-y-pyrone in trifluoroethanol (reported last year ") by preparative t.l.c. (Si02) has revealed the presence of two minor, but mechanistically significant, products. One, identified as l,3-dimethyl-6-oxabicyclo[3.1.0]pent-3-en-2-one (145), is the first isolable example of the hitherto elusive cyclopentadienone epoxides, whidi have long been postulated as intermediates in these photolyses. This dienone epoxide is the photo-precursor of the final product, i.e. the isomeric 3,6-dimethyl-a-pyrone, but not of the trifluoroethanol adduct (146). This latter product, as suggested previously, derives directly from the zwitterionic precursor of the bicyclopent-3-en-2-one (145). The other product proved to be cyclopent-l-ene-3,5-dione (147), a photo-rearrangement product of (145). 

It is believed that a reactive ground-state species, the zwitterion A, is an intermediate and that it rearranges to the observed product. To test this mechanism, generation of species A by nonphotochemical means was undertaken. a-Haloketones, when treated with strong base, ionize to such dipolar intermediates. Thus, the bromoketone 6 is a potential precursor of intermediate A ... 

Dienamines undergo 1,4 cycloaddition with sulfenes as well as 1,2 cycloaddition. For example, l-(N,N-diethylamino)butadiene (111), when treated with sulfene (generated from methanesulfonyl chloride and triethyl-amine), produces 1,4 cycloadduct 116 in an 18 % yield and di-1,2-cycloadduct 117 in a 60 % yield (160). Cycloadduct 116 was shown not to be the precursor for 117 by treating 116 with excess sulfene and recovering the starting material unchanged (160). This reaction probably takes place by way of zwitterion 115, which can close in either a 1,4 or 3,4 manner to form cycloadducts 116 and 118, respectively. The 3,4 cycloaddition would then be followed by a 1,2 cycloaddition of a second mole of sulfene to form 117. Cycloadduct 117 must form in the 3,4 cycloaddition followed by a 1,2-cycloaddition sequence rather than the reverse sequence since sulfenes undergo cycloaddition only in the presence of an electron-rich olefinic center (159). Such a center is present as an enamine in 118, but it is not present in 119. 

The (pentamethylcyclopentadienyl)zirconium amidinate unit also served as a platform for the synthesis and characterization of remarkable cationic and zwitterionic allyl zirconium complexes derived from trimethylenemethane (TMM). A direct synthetic route to the neutral precursors was found in the... 

Protonation of the TMM complexes with [PhNMe2H][B(C6Fs)4] in chlorobenzene at —10 °C provided cationic methallyl complexes which are thermally robust in solution at elevated temperatures as determined by NMR spectroscopy. In contrast, addition of BfCgFsls to the neutral TMM precursors provided zwitterionic allyl complexes (Scheme 98). Surprisingly, it was found that neither the cationic nor the zwitterionic complexes are active initiators for the Ziegler-Natta polymerization of ethylene and a-olefins. °°... 

Oxidative addition of a silyl-protected 4-(bromomethyl)phenol precursor to (tme-da)Pd(II)Me2 (tmeda = tetramethylethylenediamine), followed by ethane reductive elimination, resulted in formation of the benzylic complex 16 (Scheme 3.10). Exchange of tmeda for a diphosphine ligand (which is better suited for stabilizing the ultimate Pd(0) QM complex), followed by removal of the protecting silyl group with fluoride anion, resulted in the expected p-QM Pd(0) complex, 17, via intermediacy of the zwitterionic Pd(II) benzyl complex. In this way a stable complex of p-BHT-QM, 17b, the very important metabolite of the widely used food antioxidant BHT20 (BHT = butylated hydroxytoluene) was prepared. Similarly, a Pd(0) complex of the elusive, simplest /)-QM, 17a, was obtained (Scheme 3.10). 

FIGURE 6.16 ortho-Quinone methide 3 stabilization of the zwitterionic rotamer in a complex with /V-methyImorpholine /V-oxide (17). The zwitterionic, aromatic precursor 3a affords the common quinoid form of the o-QM 3 by in-plane rotation of the exocyclic methylene group. 

FIGURE 6.17 Oxidation of a-tocopherol (1) conventionally leads to its spiro dimer (9) via ortho-quinone methide 3 (path A). The zwitterionic o-QM precursor 3a is stabilized by NMMO in complex 17, which upon rapid heating produces small amounts of new dioxocine dimer 18 (path B). Acid treatment of 18 causes quantitative conversion into spiro dimer 9, via o-QM 3 (path C). 

FIGURE 6.19 Formula and molecular structure of the 2 1 complex 20, formed between the zwitterionic o-QM precursor derived from PMC (la) and a bis(sulfonium ylide). 

The stabilization of the zwitterionic o-QM precursors is due to electrostatic interactions. It was reasonable to assume that also the other methods of stabilizing the zwitterions might be viable, and indeed it was confirmed that both steric and electronic effects are able to stabilize such intermediates. In 5-(4-octyl)-y-tocopherol (5a-butyl-5a-propyl-a-tocopherol, 21), the octyl group acts as a flywheel, which impedes the rotation of the C-5a moiety into the ring plane as compared to the parent zwitterions with the unsubstituted exocyclic methylene group. The situation is... 

Thiopyranopyrrolizines can be prepared readily from the enamine 170 upon treatment with DMAD. Alternatively, heating of the thiacyclooctadiene derivative 171 in methanol gives the same tricycle 172, but this time as a 5 2 mixture with the (Z,E)-isomer of the precursor 171. These reactions probably involve the the intermediacy of an unstable cyclobutene and/or a zwitterionic diene, as shown in Scheme 51 <1984JA1341>. 

The formation of a small amount of naphthalene as a by-product of the reaction of benzyne with iV -methylpyrrole was noted by Wittig and Behnisch. Some related examples have recently been described. The tetrachloronaphthalen-l,4-imine (108) with benz5me gave N-methylcarbazole, which it is tempting to see as arising from the reaction of an intermediate zwitterion (compare 166) with another molecule of benzyne or, more likely, a benzyne precursor. The complementary product, 1,2,3,4-tetrachloronaphthalene, was not identified in this case. 

The formation of anthracene in reactions of 185 and 186 with benzyne, which was unexplained by Wittig et aZ., possibly is due to an alternative reaction of the intermediate zwitterion (202) with another molecule of benzjme or with a benzyne precursor. Benzyne reacted with the isoindole (206) to give the tetramethyltriptycene (208) and, in a separate run using excess of the benzyne precursor, W-benzylcarbazole. The latter product would appear to be made up of the iV-benzyl group from an intermediate anthracen-9,10-imine (207) and two molecules of benzyne. Mass spectral evidence also implicated the adduct 207, and the formation of 208 was attributed to benzyne-induced deamination of 207 to 1,4,9,10-tetramethylanthracene, which was trapped by further addition of benzyne across the 9- and 10-positions. 

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