Bis(2,2'-bipyridyl-κ(2)N,N')dichlorido-rhodium(III) perchlorate.

The asymmetric unit of the title compound, [RhCl(2)(C(10)H(8)N(2))(2)]ClO(4), consists of one unit of the cationic complex [RhCl(2)(bipy)(2)](+) and one uncoordinated perchlorate anion. The Rh(III) atom is coordinated by four N atoms from two bipyridyl ligands and two Cl atoms, forming a distorted octa-hedral environment. The Cl ligands are cis. Two intramolecular C-H⋯Cl hydrogen bonds occur in the cationic complex . In the crystal, mol-ecules are linked together by a hydrogen-bond network involving the H atoms of bipyridyl rings and perchlorate anions. An O atom of the perchlorate anion is disordered over two sites, with an occupancy-factor ratio of 0.78 (3):0.22 (3).

Enantioselective multicomponent synthesis of fused 6-5 bicyclic 2-butenolides by a cascade heterobicyclisation process.

The successive coupling of an alkoxy(aryl/heteroaryl)carbene complex of chromium with either a ketone or an imide lithium enolate and then a 3-substituted (H, TMS, PhCH(2), PhCH(2)CH(2), Me) propargylic organomagnesium reagent has afforded novel hydroxy-substituted bicyclic [4.3.0]-γ-alkylidene-2-butenolides with three modular points that has allowed the efficient introduction of molecular complexity, including a homopropargylic alcohol core. The selective formation of these five- or six-component heterobicyclisation products is the result of the regioselective integration of the Grignard reagent as a propargyl fragment followed by a cascade CO/alkyne/CO insertion, ketene trapping and elimination sequence. By using lithium enolates of chiral N-acetyl-2-oxazolidinones and the corresponding propargylic organocerium reagents, both enantiomers of these bicyclic heterocycles were efficiently prepared with very high enantiomeric purity. Architecturally, these fused bicyclic butenolides are characterised by a highly unsaturated and oxygenated core and they exhibit strong blue fluorescence in solution.

N,N'-Dibenzyl-N''-(2,4-difluoro-benzo-yl)-N,N'-dimethyl-phospho-ric triamide.

In the title mol-ecule, C(23)H(24)F(2)N(3)O(2)P, the P atom is in a distorted tetra-hedral P(=O)(N)(N)(2) environment, with the bond angles around the P atom in the range 106.78 (11)-114.10 (13)°. The phosphoryl and carbonyl groups, which are separated by an N atom, adopt an anti orientation relative to each other. In the C(=O)NHP(=O) fragment, the P-N bond is longer [1.683 (2) Å] and the O-P-N angle is smaller [106.78 (11)°] than the other P-N bonds [1.613 (2) and 1.632 (2) Å] and O-P-N bond angles [114.10 (13) and 110.83 (12)°], respectively. The N atoms have sp(2) character. In the crystal, pairs of P=O⋯H-N hydrogen bonds form inversion dimers with R(2) (2)(8) ring motifs.

N,N'-Dibenzyl-N,N'-dimethyl-N''-(2-phenyl-acet-yl)phospho-ric triamide.

The P atom in the title mol-ecule, C(24)H(28)N(3)O(2)P, is in a distorted tetra-hedral P(=O)(N)(N)(2) environment. The phosphoryl group and the NH unit adopt a syn orientation with respect to each other and the N atoms have sp(2) character. The P-N bonds in the P(O)[N(CH(3))(CH(2)C(6)H(5))](2) unit are shorter than the P-N bond in the C(=O)NHP(=O) fragment. An intra-molecular C-H⋯O hydrogen bond occurs. In the crystal, pairs of P=O⋯H-N hydrogen bonds form centrosymmetric dimers. C-H⋯O contacts are also observed. Four C atoms of two benzene rings are disordered over two alternative sites with an occupancy ratio of 0.523 (12):0.427 (12).

N,N'-Dibenzyl-N,N'-dimethyl-N''-(4-nitro-benzo-yl)phospho-ric triamide.

The P atom in the title compound, C(23)H(25)N(4)O(4)P, is in a slightly distorted tetra-hedral coordination environment and the N atoms show sp(2) character. The phosphoryl group and the NH unit are syn with respect to each other. In the crystal, pairs of inter-molecular N-H⋯O(P) hydrogen bonds form centrosymmetric dimers.

N-Benzoyl-N',N''-dicyclo-hexyl-phospho-ric triamide.

In the title compound, C(19)H(30)N(3)O(2)P, the central P atom has a distorted tetra-hedral configuration. The N atoms in both cyclo-hexyl-amide moieties exhibit a slight deviation [0.32 (7) and 0.44 (6) Å] from planarity, while the benzoyl-amide N atom is planar [0.11 (3) Å]. In the crystal, mol-ecules are linked via N-H⋯O(P) and N-H⋯O(C) hydrogen bonds, forming R(2) (2)(10) rings within linear arrangements parallel to the b axis.

5-Hy-droxy-7-phenyl-5-(prop-2-yn-1-yl)-5,6-dihydro-1-benzofuran-2(4H)-one monohydrate.

In the title compound, C(17)H(14)O(3)·H(2)O, the six-membered ring, which adopts a half-chair conformation, makes a dihedral angle of 24.3 (2)° with the phenyl ring. In the crystal, the components are linked by O-H⋯O hydrogen bonds involving the water mol-ecule, and the hy-droxy and carbonyl groups of the organic compound. These inter-actions form a square-like supra-molecular synthon unit which propagates as chains parallel to the crystallographic b axis. A C-H⋯O interaction also occurs.

(1RS,2RS,3RS)-1,2-Dimeth-oxy-3-methyl-2-phenyl-1-(2-thien-yl)cyclo-propane.

In the title compound, C(16)H(18)O(2)S, a new cis-1,2-dimethoxy-cyclo-propane, the two meth-oxy groups are in a cis configuration and in trans positions with respect to the H atom and the phenyl and thienyl rings on the cyclo-propyl group. The mol-ecular packing is dominated by weak inter-molecular C-H⋯O inter-actions, allowing the formation of zigzag chains propagating parallel to the c axis. The dihedral angle between the aromatic rings is 86.12 (8)°.

1,4-Bis(methyl-sulfan-yl)naphthalene.

The mol-ecule of the title compound, C(12)H(12)S(2), is close to planar, with the methyl C atoms deviating by 0.019 (1) and 0.221 (2) Šfrom the naphthalene mean plane. In the crystal structure, the shortest S⋯S contact of 3.6864 (9) Šis longer than the van der Waals contact distance.

Asymmetric deprotonation-substitution of N-Pop-benzylamines using [RLi/(-)-sparteine]. Enantioselective sequential reactions and synthesis of N-heterocycles.

Pop-directed asymmetric deprotonation of benzylic amines using [n-BuLi/(-)-sparteine] provides an efficient method for the synthesis of chiral NC alpha and NC alpha,alpha' derivatives with total selectivity with respect to competing allylic and ortho lithiation. The method described herein offers a straightforward route of accessing chiral N-Pop-protected nitrogen heterocycles.