Preparation and crystal structures of a series of titanium(III) 9-BBN hydroborate complexes containing Ti...H agostic interactions

9-BBN hydroborate complexes Ti{(mu-H)2BC8H14}3(THF)2 (1), Ti{(mu-H)2BC8H14}3(OEt2) (2), and [K(OEt2)4]-[Ti{(mu-H)2BC8H14}4] (4) were formed from the reaction of TiCl4 with K[H2BC8H14] in diethyl ether or THF. Ti{(mu-H)2BC8H14}3(PhNH2) (3) was isolated from the reaction of 2 with aniline in diethyl ether. In the formation of these complexes, Ti(IV) is reduced to Ti(III). The coordinated diethyl ether in 2 can be displaced by the stronger bases THF and aniline, to form 1 and 3, respectively. All of the compounds were characterized by single-crystal X-ray diffraction analysis. In complex 1, which contains two coordinated THF ligands, the titanium possesses a 17 electron configuration and there is no evidence for agostic interaction. Complexes 2 and 3 contain only one coordinated ether or aniline ligand, and the titanium possesses a 15 electron configuration. In these compounds, a C-H hydrogen on an alpha carbon on the BC8H14 unit of a 9-BBN hydroborate ligand forms an agostic interaction with the titanium. Criteria for assessing the existence of agostic interactions are discussed. As the potassium salt, the anion of complex 4 is more stable than the complexes 1-3. Organometallic anions of the type [ML4]- for titanium(III) are rare.     

The Asymmetric Synthesis of Fused Cyclopentenone Ring Systems: A formal asymmetric total synthesis of (−)-isocomene

Optically active tricyclic oxazolidine lactams 10 have been prepared using two different routes (Scheme 1). They can be obtained by acid-mediated intramolecular cyclization of bicyclic lactams 13 via their acyliminium intermediates producing appended five-, six-, and seven-membered tricyclic systems. Alternatively, 10 can be prepared by cyclocondensation of chiral amino alcohols with cyclopentane-1,2-dicarboxylic acids 12 to give the imide which is reduced or alkylated to the amino alcohols and cyclized to a diastereoisomer mixture of 10 . Alkylation of 10 (R″ = H) via its enolate gives stereospecifically α-quaternary products 10 ( R ″ = alkyl). Degradation of the latter with MeLi or Red-Al® followed by mild acid hydrolysis and aldol cyclization produces the bicyclic ketones 14 and 15 as 1:1 mixtures, readily separated and isolated in > 99% ee. This sequence produced a known non-racemic intermediate 69 for the synthesis of (?)-isocomene.     

Europium(II) and ytterbium(II) cyclic organohydroborates: an europium(II) complex with an agostic interaction

Lanthanide bis((cyclooctane-1,5-diyl)dihydroborate) complexes (THF)(4)Ln[(micro-H)(2)BC(8)H(14)](2) (Ln = Eu, 1; Yb, 2) were synthesized by a metathesis reaction between (THF)(x)()LnCl(2) and K[H(2)BC(8)H(14)] in THF in a 1:2 molar ratio. Attempts to prepare the monosubstituted lanthanide cyclic organohydroborates (THF)(x)LnCl[(micro-H)(2)BC(8)H(14)] were unsuccessful. On the basis of the molecular structure and IR spectrum of 1, there is an agostic interaction between Eu(II) and one of the alpha-C-H hydrogens from the [(micro-H)(2)BC(8)H(14)] unit. No such interaction was observed for 2. The coordinated THF in 1 and 2 can be removed under dynamic vacuum, but the solvent ligands remain bound to Yb when 2 is directly dissolved in Et(2)O or toluene. In strong Lewis basic solvents, such as pyridine or CH(3)CN, attack of the Yb-H-B bridge bonds results. Decomposition of 2 to the 9-BBN dimer in CD(2)Cl(2) was observed by (11)B and (1)H NMR spectroscopies. Compound 2 was reacted with 2 equiv of the hydride ion abstracting reagent B(C(6)F(5))(3) to afford the solvent-separated ion pair [Yb(THF)(6)][HB(C(6)F(5))(3)](2) (3). Complexes 1, 2, and 3 were characterized by single-crystal X-ray diffraction analysis. Crystal data: 1 is orthorhombic, Pna2(1), a = 21.975(1) A, b = 9.310(1) A, c = 16.816(1) A, Z = 4; 2 is triclinic, P1, a = 9.862(1) A, b = 10.227(1) A, c = 10.476(1) A, alpha = 69.87(1) degrees, beta = 76.63(1) degrees, gamma = 66.12(1) degrees, Z = 1; 3.Et(2)O is triclinic, P1, a = 13.708(1) A, b = 14.946(1) A, c = 17.177(1) A, alpha = 81.01(1) degrees, beta = 88.32(1) degrees, gamma = 88.54(1) degrees, Z = 2.     

An asymmetric approach to spirocylic systems: a formal synthesis of zizaene

A general route to enantiopure spirocarbocycles is described. The use of various chiral bicyclic lactams 1 that have been doubly alkylated with olefinic halides gives good yields of alpha,alpha-disubstituted chiral lactams 2 which were cyclized to spiro-olefins using ring closure metathesis methodology (Grubbs' catalyst). These spirolactams 3, formed in generally excellent yields, were shown to be smoothly transformed into spirocyclopentenone 6, spirocyclohexenone, 7, and spirolactams 8. Further demonstration of this spirocyclization methodology was featured in a formal synthesis of zizaene, by preparing in enantiomeric form the Coates' intermediate 21. This synthetic effort provided additional examples of the synthetic versatility of chiral bicyclic lactams 2a,b.     

Asymmetric and nonasymmetric addition of RLi and RMgX to 3-methoxynaphthalen-2-yl oxazolines and imines. An approach to substituted 2-tetralones

Chiral and achiral 3-methoxynaphthalen-2-yl oxazolines 4a,b failed to undergo an aromatic nucleophilic displacement of the 3-methoxy group with organolithium reagents and instead afforded dihydronaphthalenes 9 and 14 in 30-95% yield. Dihydronaphthalenes 9 (racemic) and 14 (nonracemic) were easily converted into the corresponding aldehydes 15. Alternatively, aldehydes 15 were prepared via tandem addition of Grignard reagents to imines 17 in 50-65% yield. Aldehydes 15 served as precursors to 3,3, 4-trisubstituted 2-tetralones 16. Use of methyl chloroformate to trap the azaenolate derived from 17f and i-PrMgCl afforded, in 65% yield, a versatile synthetic intermediate 23 which may serve to access 4-alkyl-, 3,4-dialkyl-, 3,4-disubstituted and 3,3, 4-trisubstituted 2-tetralones with diverse substitution patterns.     

Lanthanide-transition-metal carbonyl complexes: new [Co4(CO)11]2- clusters and lanthanide(II) isocarbonyl polymeric arrays

Two types of Ln(II)-Co(4) isocarbonyl polymeric arrays, [(Et(2)O)(3)(-)(x)()(THF)(x)()Ln[Co(4)(CO)(11)]]( infinity ) (1-3; x = 0, 1) and [(THF)(5)Eu[Co(4)(CO)(11)]]( infinity ) (4), were prepared and structurally characterized. Transmetalation involving Ln(0) and Hg[Co(CO)(4)](2) in Et(2)O yields [(Et(2)O)(3)Ln[Co(4)(CO)(11)]]( infinity ) (1, Ln = Yb; 2, Ln = Eu). Dissolution of the solvent-separated ion pairs [Ln(THF)(x)()][Co(CO)(4)](2) (Ln = Yb, x = 6; Ln = Eu) in Et(2)O affords [(Et(2)O)(2)(THF)Yb[Co(4)(CO)(11)]]( infinity ) (3) and [(THF)(5)Eu[Co(4)(CO)(11)]]( infinity ) (4). In these reactions, oxidation and condensation of the [Co(CO)(4)](-) anions result in formation of the new tetrahedral cluster [Co(4)(CO)(11)](2)(-). The two types of Ln(II)-Co(4) compounds contain different isomers of [Co(4)(CO)(11)](2)(-), and, consequently, the structures of the infinite isocarbonyl networks are distinct. The cluster in [(Et(2)O)(3)(-)(x)()(THF)(x)()Ln[Co(4)(CO)(11)]]( infinity ) (1-3) possesses pseudo C(3)(v)() symmetry (an apical Co, three basal Co atoms; one face-bridging, three edge-bridging, seven terminal carbonyls) and connects to Ln(II) centers through eta(2),micro(4)- and eta(2),micro(3)-carbonyls to generate a 2-D puckered sheet. In contrast, [(THF)(5)Eu[Co(4)(CO)(11)]]( infinity ) (4) incorporates a C(2)(v)() symmetric cluster (two unique Co environments; two face-bridging, one edge-bridging, eight terminal carbonyls), and isocarbonyl linkages (eta(2),micro(4)-carbonyls) to Eu(II) atoms create a 1-D zigzag chain. Complexes 1-4 contain the first reported eta(2),micro(4)-CO bridges between a Ln and a transition-metal carbonyl cluster. Infrared spectroscopic studies revealed that the isocarbonyl associations to Ln(II) persist in solution. The solution structure and dynamic behavior of the [Co(4)(CO)(11)](2)(-) cluster in 1 was investigated by variable-temperature (59)Co and (13)C NMR spectroscopies.     

trans‐3‐Ethyl‐cis‐2,6,6‐trimethyl‐4‐oxocyclohexanecarboxylic acid: an intermediate in the synthesis of a highly potent estrogen

The title compound, C₁₂H₂₀O₃, (IV), the ethyl ester of which is an intermediate in the synthesis of a compound reported to be highly estrogenic, has been prepared. After the initial steps reported for the synthesis of this ester intermediate were followed, it was converted into the crystalline acid, (IV), for X‐ray analysis. It was verified that (IV) was racemic when prepared. X‐ray analysis showed that anti‐hydrogenation of the double bond had occurred in the synthesis, making the orientation of the carboxyl group cis to the 2‐methyl group and trans to the 3‐ethyl group. NMR spectroscopy showed that the stereochemistry of (IV) was identical with that of its ester precursor. While the earlier report did not note the stereochemistry of this ester, it pointed out that the estrogenic product derived from it possessed the opposite carboxyl‐2‐methyl orientation, i.e.trans, although no X‐ray analysis was performed. In the light of these results and the importance of correlating biological activity with compound structure, the unequivocal characterization of the highly estrogenic compound is warranted.     

Shock compression of [001] single crystal silicon

Silicon is ubiquitous in our advanced technological society, yet our current understanding of change to its mechanical response at extreme pressures and strain-rates is far from complete. This is due to its brittleness, making recovery experiments difficult. High-power, short-duration, laser-driven, shock compression and recovery experiments on [001] silicon (using impedance-matched momentum traps) unveiled remarkable structural changes observed by transmission electron microscopy. As laser energy increases, corresponding to an increase in peak shock pressure, the following plastic responses are are observed: surface cleavage along {111} planes, dislocations and stacking faults; bands of amorphized material initially forming on crystallographic orientations consistent with dislocation slip; and coarse regions of amorphized material. Molecular dynamics simulations approach equivalent length and time scales to laser experiments and reveal the evolution of shock-induced partial dislocations and their crucial role in the preliminary stages of amorphization. Application of coupled hydrostatic and shear stresses produce amorphization below the hydrostatically determined critical melting pressure under dynamic shock compression.