Four-membered ring compounds synthesis

Summary The formation, reactivity, and cycloaddition behavior of neopentylsilenes towards suitable reaction partners is described. Especially l,l-dichloro-2-neopentylsilene. Cl2Si=CHCH2Bu (2) - easily obtained from vinyltrichlorosilane and LiBu - is a useful building block for the synthesis of SiC four membered ring compounds. These can be converted into the isomeric Diels-Alder and retro ene products upon thermolysis reactions. The mode of the silenes cycloaddition reactions ([4+2] vs [2+2] addition) can be directed by either the substitution pattern at the Si=C moiety, the choice of reaction partners or the conditions. Furthermore the products resulting from cycloaddition reactions open up a wide variety of following reactions, which possibly will lead to new organosilicon materials or pharmaceutical compounds. 

If the cycloaddition and cycloreversion steps occurred under the same conditions, an equilibrium would establish and a mixture of reactant and product olefins be obtained, which is a severe limitation to its synthetic use. In many cases, however, the two steps can very well be separated, with the cycloreversion under totally different conditions often showing pronounced regioselectivity, e.g. for thermodynamic reasons (product vs. reactant stability), and this type of olefin metathesis has been successfully applied to organic synthesis. In fact, this aspect of the synthetic application of four-membered ring compounds has recently aroused considerable attention, as it leads the way to their transformation into other useful intermediates. For example aza[18]annulene (371) could be synthesized utilizing a sequence of [2 + 2] cycloaddition and cycloreversion. (369), one of the dimers obtained from cyclooctatetraene upon heating to 100 °C, was transformed by carbethoxycarbene addition to two tetracyclic carboxylates, which subsequently lead to the isomeric azides (368) and (370). Upon direct photolysis of these, (371) was obtained in 25 and 28% yield, respectively 127). Aza[14]annulene could be synthesized in a similar fashion I28). 

ROP of cyclic carbosilanes is one of the most promising techniques for the synthesis of well-defined polycarbosilanes. ROP of four-membered ring compounds, 1,3-disilacyclobutanes, and monosilacyclobutanes, as well as copolymerizations of mixtures of monomers, have been widely investigated in the last decades <1996JOMl, B-1996MI7621, B-2000MI247>. 

Photochemical reactions provide a classical access to four-membered ring compounds that generate major interest in organic synthesis, notably as intermediates in multistep syntheses. The [2 + 2] photocycloaddition of a,(3-unsaturated carbonyl and carboxyl compounds with alkenes and [2 + 2] photocydoaddition of ketones with alkenes (the Paterno-Buchi reaction) are discussed in Chapters 6 and 7, respectively. Yet, aside from these transformations, a variety of further reactions provides a systematic access to four-membered rings that possess a wide structural variation. Four-membered ring compounds may also be created via less-systematic photochemical transformations, many of which can be carried out without additional chemical activation. As a consequence, such transformations are rendered not only very convenient but also extremely interesting within the context of green chemistry. ... 

Closely related to this synthesis of the eight-membered ring is a route to the four-membered ring compound l,l,3,3-tetramethyl-l,3-disilacyclo-butane (40). The final step is shown in Eq. (10) ring closure is brought about with Mg in diethyl ether with a yield of 70% ... 

In [2+2] cycloaddition reactions of carbon cumulenes, often only one four-membered ring compound is obtained. This reaction is of considerable importance in the synthesis of 8-lactams from ketenes and C=N double bond containing substrates. The j8-lactam structure is present in a variety of antibiotics. Also, j8-thiolactams are obtained from thioketenes and imines. 

In the presence ofnickel(O) catalysts, ethyl cyclopropylideneacetate participated in [3+2+2], [4+3], and [4+3+2] annulation to furnish medium-sized carbocy-cles (Table 2.5) [116]. Synthesis of seven-membered ring compounds by formal o-bond metathesis between the MCP and four-membered ring compounds was also achieved [117]. 

Intramolecular amination with allylic acetates is used for the synthesis of cyclic alkaloids 175]. Cyclization of 293 affords the six-membered ring compound 294 rather than a four-membered ring. The reaction is particularly... 

Unfortunately, both the lithium and the sodium compound are stable even when melted, destilled or sublimed. Therefore, Si-O four-membered ring systems are not accessible by this method of synthesis up to now. 

Several relevant papers and review articles have appeared recently. These contain reports on the mechanism and kinetics of the ene reaction of ADC compounds,243-245 examples of four-membered ring formation,246-247 other cycloadditions of ADC compounds,248-252 the synthesis of azoalkanes,253 the use of chiral l,2,4-triazole-3,5-diones,254 and the use of the DEAZD/PI13P reagent in organic synthesis.255... 

The coordination of the phosphine P(ft-Pr)2Ph to the Lewis acidic Ga center is essential for the synthesis of both compounds. In the absence of any Lewis base, the most likely reaction product would be the heterocubane [ClGaSbSi(/-Pr)3]4. However, in analogy to the results observed for reactions of heterocycles [R MER with Lewis bases, leading to base-stabilized monomeric compounds, both the formation of 84 and 85 can be explained by reaction of such a heterocubane intermediate with the phosphine base. According to the description of heterocycles as head-to-tail adducts, heterocubanes may be described as Lewis acid-base adducts between two four-membered rings as shown in Fig. 45. 

Still another possibility in the base-catalyzed reactions of carbonyl compounds is alkylation or similar reaction at the oxygen atom. This is the predominant reaction of phenoxide ion, of course, but for enolates with less resonance stabilization it is exceptional and requires special conditions. Even phenolates react at carbon when the reagent is carbon dioxide, but this may be due merely to the instability of the alternative carbonic half ester. The association of enolate ions with a proton is evidently not very different from the association with metallic cations. Although the equilibrium mixture is about 92 % ketone, the sodium derivative of acetoacetic ester reacts with acetic acid in cold petroleum ether to give the enol. The Perkin ring closure reaction, which depends on C-alkylation, gives the alternative O-alkylation only when it is applied to the synthesis of a four membered ring ... 

The stereoselective or stereospecific formation of these compounds and their interaction with butyllithium was studied with the help of NMR. Paquette and Freeman first applied asymmetric induction to the synthesis of four-membered rings, especially with the sulfene-enamine 2 -F 2 cycloaddition. The in situ generation of sulfene 68 by dehydrochlorination with butyllithium of the sulfonyl chloride allowed the formation of cycloadduct 69 in 88 % yield. In a variation, the sulfene may be generated by base-induced... 

Synthesis of Compounds with a Central Four-Membered Ring... 

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