Enynes acyclic

For acyclic enynes, there is a pronounced effect of the substitution pattern on the reactivity (Fig. 9). Substrates 14 with = H could only be rearranged by catalyst... 

Equally to ferrate 38 ferrates 39 and 40 also catalyze Alder-ene cycloisomeriza-tions [17]. Compared to 38, they require somewhat longer reaction times, possibly due to the chelating cod-hgand, which is more difficult to substitute by the en)me. The presence of cod in the reaction turns out to be of advantage with more demanding substrates like acyclic enynes with a terminal aUcene moiety where ferrate 38 is not reactive. Cod is assumed to stabilize the catalyst in its resting state as ancillary hgand. 

The sequential double migratory insertion of CO into acydic and cydic diorganozircono-cene complexes through acylzirconocene and ketone—zirconocene species provides a convenient procedure for preparing acyclic and cyclic ketones (Scheme 5.6) [8], Thus, the bi-cydic enones from enynes can be obtained through CO insertion into zirconacyclopen-tenes followed by a subsequent rearrangement (Scheme 5.7). The scope and limitations of this procedure have been described in detail elsewhere [8d]. This procedure provides a complementary version of the well-known Pauson Khand reaction [9]. 

Cycloisomerization represents another approach for the construction of cyclic compounds from acyclic substrates, with iridium complexes functioning as efficient catalysts. The reaction of enynes has been widely studied for example, Chatani et al. reported the transformation of 1,6-enynes into 1-vinylcyclopentenes using [lrCl(CO)3]n (Scheme 11.26) [39]. In contrast, when 1,6-enynes were submitted in the presence of [lrCl(cod)]2 and AcOH, cyclopentanes with two exo-olefin moieties were obtained (Scheme 11.27) [39]. Interestingly, however, when the Ir-DPPF complex was used, the geometry of olefinic moiety in the product was opposite (Scheme 11.28) [17]. The Ir-catalyzed cycloisomerization was efficiently utilized in a tandem reaction along with a Cu(l)-catalyzed three-component coupling, Diels-Alder reaction, and dehydrogenation for the synthesis of polycyclic pyrroles [40]. 

Transition metal-catalyzed carbocycUzation reactions of tethered diene, enyne, diyne, and vinylallene derivatives represent an important class of transformations in synthetic organic chemistry. This may be attributed to the abihty to significantly increase molecular complexity through the highly selective combination of acyclic components, thereby facilitating the synthesis of complex polycychc products. Recently, rhodium-catalyzed carbocyclization reactions have attracted significant attention due to their immense synthetic versatility and the unique selectivities observed over a range of different transformations. This chapter provides an account of recent developments in rhodium-catalyzed [4-1-2] and [4-i-2-t2] carbocyclization reactions. 

Hydrogenated derivatives of this system have been prepared from acyclic enyne precursors (Scheme 75) by ringclosing metathesis, followed by [4-1-2] cycloaddition of the resulting diene with diethyl azodicarboxylate <2003S2017>. 

Phase transfer-catalyzed reactions have recently been employed to dehydro-halogenate gem-dihalocyclopropanes [156, 157]. Thus, 1-methylene-2-vinylcyclo-propane has been prepared from l,l-dichloro-2-ethyl-3-methylcyclopropane in 60 % yield. Under the reactipn conditions (solid KOH, DMSO in the presence of dibenzo-18-crown-6, 100-130 °C) further transformations may take place, however. For example, monoalkylated cyclopropanes have been converted to mixtures of acyclic enynes and conjugated trienes. And 7,7-dichloronorcarane is converted to toluene under these conditions. 

Scheme 15 Mechanisms of the palladium-catalyzed cycloisomerization of acyclic 1, -enynes ( = 6,7) [66-68]...

The most recent contribution in this area is by Shea who prepared tricyclic oxygen containing heterocycles from acyclic enynes 82 using a combination of intramolecular Nicholas and PKRs. They constructed [5.7.5] and [5.8.5] (83-84) systems involving the formation of a complexed cyclic alkyne. They used several PKR conditions that give different yields and diastereo-selectivities. Due to the strain of the intermediate, [5.6.5] systems (85) were obtained in poor yields (Scheme 24) [121]. 

In connection with the aforementioned reaction, Shea et al. reported the synthesis of [5,8,5]- and [5,7,5]-tricyclic oxygen-containing heterocycles via tandem Nicholas [35] and Pauson-Khand [23,24] reactions of acyclic enynes [36]. A typical Nicholas/[2 + 2 + 1] sequence is depicted in Scheme 12. 

Diver has recently reported new entries for the assembly of tetracyclic derivatives [89]. Interestingly, ruthenium metathesis-type catalysts have also given birth to tricyclic derivatives incorporating a cyclopropane from di-enynes [90]. Cationic gold-based catalysts have proven to be even more reactive promotors of various reactions resulting from a preliminary electrophilic activation [91]. They also allow the formation of tetracyclic derivatives 140 from acyclic precursors 139 at low temperature and as single diastereomers. In one case, the minor metathesis diene 141 was isolated. Tetracyclic products... 

Reactions involving Acyclic Heteroatom-containing Enynes... 

Enyne titanium complexes are synthesized when enynes are treated with Ti(OPr1)2( 72-propene). These species add aldehydes, ketones, and chiral imines to generate multiple stereogenic centers in an acyclic system. Numerous methods for the stereoselective construction of two stereogenic centers are known, although those for more than three in one asymmetric procedure are less common.195... 

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