Bicyclo -deca-1 ,7-triene

Chelate complexes of the type [PdX2(diene)] (X = Cl, Br) are readily formed by the dienes hexa-1,5-diene (124), bicyclo 2,2,lJhepta-2,5-diene (1, 7) tricyclo[4,2,2,0]-deca-triene and -diene derivatives (10), cyclo-octa-1,5-diene and dicyclopentadiene, but not dipentene (43). These may be converted to complexes of the types [Pd2X2(dieneOR)2] and [PdCl(dieneOR)-(amine)] (R = alkyl) (43), and their properties indicate that they have similar structures to the platinum complexes (XXXI) and (XXXIII). 

Intramolecular cyclopropanation of 4-aryl-1 -diazo-2-butanones 240 allows construction of the bicyclo[5.3.0]decane framework 12). In a reaction sequence analogous to that described above for the intermolecular ketocarbenoid reaction, bicyclo-[5.3.0]deca-l,3,5-trien-8-ones 241 are formed. They rearrange to the conjugated isomers 242 at the high temperatures needed if the reaction is catalyzed by copper 2311 or CuCl 232), but can be isolated in excellent yield from the Rh2(OAc)4-promoted reaction which occurs at lower temperature 233... 

IO-Aza-tricydo 3.3.2.02,8]deca-3,6-dien 9-Oxo- EI7b, 1219 (10-Oxo-9-aza-bicyclo[4.2.2]deca-2,4,7-trien/hv)... 

A1CI3 En) Bicyclo 6.2.0 deca-2,4,6-trien E17e, 241 (Cyclooctatetraen +... 

Thia-4-aza-bicyclo 5,3,0 deca-l7,2,4-trien 5-Diethylamino-E16c, 182 (6-Nj —1-benzothio-phen-Der./Amin)... 

Skeletal rearrangements are rare, but are found for strained bi- and polycyclic alkenes, e.g., bullvalene , bicyclo[4.2.2]deca-2,4,7,9-tetraene , 4,5-exo-trimethylene-2-norbornene , 6-methylenebicyclo[3.1.1]heptane ", 5-methylbicyclo[2.1.1] hexene N-benzyl-9-aza-bicyclo[4.2.2]deca-2,4,7-triene , dibenzobicyclo[2.2.2]-octatriene derivatives and bornylene ... 

Various bi- and oligocyclic ring systems, such as norcaradiene (1 bicyclo[4.1.0]hepta-2,4-diene), bicyclo[6.1.0]nona-2,4,6-triene (2), bullvalene (3 tricyclo[3.3.2.0 ]deca-3,6,9-triene), semibul-Ivalene (4 tricyclo[3.3.0" ]octa-2,7-diene), barbaralone (5 tricyclo[3.3.1.0 ]nona-3,6-dien-10-one) and many other systems containing divinylcyclopropane subunits, exhibit interesting transition metal mediated reaction pathways leading to new carbon skeletons. ... 

Bicyclo[4.4.0 deca-2,4,7-triene 2310 Bicyclo[6.1,0 nona-2,4,6-trienc... 

Bicyclo 5.2.1)deca-2,4,9-triene 1,7-Diacetoxy- 2671 Bicyclo 3.2.1 octa-2,6-dienc... 

Largely similar behavior is evident in the dimerizations of c ,franj-l,3-cyclooctadiene (38), tranj,ciJ-2,4-cyclooctadienone (39) ° and bicyclo[4.2.2]deca-3-franj,7,9-triene (40). ... 

The trons-cycloalkenes 37a, 67, and trans-cyclononene 227 react with diironnonacarbonyl 228 to form the tetracarbonyliron(O) complexes 229-231 with the frans-cyclooctene complex 229 being significantly more stable than that of trons-cyclodecene 231 (177). The bicyclic triene 232 reacts with 228 preferentially at one of the trans double bonds of the trans, trans- cy-clodecadiene substructure. In line with the expected stability, the trans, cis-cycloocta-1,5-diene 234 and trans, ris-cycloocta-1,3-diene 236 react with 228 exclusively at the trans double bond to give the complexes 235 and 237. In the complex 238, tetracarbonyliron(O) is bonded to the bridgehead double bond of bicyclo[4.3.2]deca-7,9-diene (184b) (177). 

Tricyclo[3.3.2.(H>< ]deca-2,7,9-trienes from bicyclo[4.2.2]decatetraenes... 

The purely thermal processes that are involved include the formation of cw-9,10-dihydronaphthalene (C9,10) from bullvalene (BV), bicyclo[4.2.2]decatetrene (422) and its intramolecular Diels-Alder adduct, tetracyclo[4.4.0.0 0 ]decadiene (TCD), from lumibullvalene (LBV), isobullvalene (IBV), tricyclo[5.3.0.0 ]deca-3,5,9-triene (TDT), and isolumibullvalene (ILBV), from basketene (BSK), NHC, TRQ, and the syn and anti isomers of tricyclo[4.4.0.0 ]decatriene (S and A, respectively), and from all c/ -cyclodecapentaene (C5), snoutene (SNT), and diademane (DIA). A more recent review includes many heats of formation and enthalpies of activation ... 

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