Lithium cadmate-mediated deprotonative metalation of anisole: experimental and computational study

International audienceLithium cadmates bearing different ligands were compared with efficient (TMP)(3)CdLi (TMP = 2,2,6,6-tetramethylpiperidino) for their ability to deprotometalate anisole. The generated arylcadmates were evidenced using I(2). The results show that it is possible to replace only one of the TMP (with a piperidino, a diisopropylamino, a butyl, or a sec-butyl) without important yield drop. In the light of DFT calculations, reaction pathways were proposed for the deprotocadmations of anisole using a triamino, an alkyldiamino, and an aminodialkyl cadmat

Diastereoselective deprotonative metalation of chiral ferrocene derived acetals and esters using mixed lithium-cadmium and lithium-zinc combinations

International audienceIn situ bimetal combinations, and notably those prepared from MCl2(radical dotTMEDA) (M=Zn, Cd; TMEDA=N,N,N′,N′-tetramethylethylenediamine) and Li(TMP) (3 or 4 equiv, TMP=2,2,6,6-tetramethylpiperidino), were screened for their ability to diastereoselectively deprotonate ferrocenes bearing a chiral group. The ferrocene carboxylate generated from diacetone-d-glucose afforded the corresponding 2-iodo derivative in 74% yield with 90% de (SP diastereoisomer) using the base generated from CdCl2 and Li(TMP) (3 equiv), and in 85% yield with 91% de (SP diastereoisomer) through a double asymmetric induction using a chiral lithium-zinc base generated from ZnCl2*TMEDA and lithium (R)-bis(1-phenylethyl)amide (4 equiv). In contrast, using a combination prepared from ZnCl2 and Li(TMP) (4 equiv) with the ferrocene carboxylate obtained from 6-(tert-butoxycarbonylamino)-6-deoxy-3-O-methyl-1,2-O-isopropylidene-α-d-glucofuranose led to the RP-iodo derivative in 57% yield after separation. Suzuki coupling was performed satisfactorily on the isolated SP and RP diastereoisomer iodoesters

Synthesis of both enantiomers of ferrocene[1,2-c]1H-quinolin-2-one by diastereoselective deproto-zincation of sugar-derived ferrocene esters

This research has also been performed as part of the Indo-French "Joint Laboratory for Sustainable Chemistry at Interfaces". The calculations were performed by using the RIKEN Integrated Cluster of Clusters (RICC) facility.International audienceDiastereoselective deproto-metallation of several sugar-derived ferrocene esters using lithium-zinc bases was studied. While bis[(R)-1-phenylethyl]amino as ligand afforded the diacetone-D-glucose-based (SP)-2-iodoferrocene ester in 91% de after iodination, the RP was synthesized from α-D-glucofuranose using 2,2,6,6-tetramethylpiperidino as ligand. Both (RP)- and (SP)-ferrocene[1,2-c]1H-quinolin-2-one were reached by subsequent cyclizing coupling, albeit their racemization was noted

Structural effects in lithiocuprate chemistry:the elucidation of reactive pentametallic complexes

TMPLi (TMP=2,2,6,6-tetramethylpiperidide) reacts with Cu(I) salts in the presence of Et(2)O to give the dimers [{(TMP)(2)Cu(X)Li(2)(OEt(2))}(2)] (X=CN, halide). In contrast, the use of DMPLi (DMP=cis-2,6-dimethylpiperidide) gives an unprecedented structural motif; [{(DMP)(2)CuLi(OEt(2))}(2)LiX] (X=halide). This formulation suggests a hitherto unexplored route to the in situ formation of Gilman-type bases that are of proven reactivity in directed ortho cupration

Changes in Japanese-style Management considering Gender Perspective

especially personnel management as the keys to understanding Japanese companies ’ success generally known for 3 main characteristic management practices 2 Lifetime employment companies ’ interest in the long ter

日本の職場におけるジェンダー平等に向けた取り組み

This study explored the effects of organizational gender equality activities in Japanese workplaces. The Coalition for Advancing Women in Fukuoka found that setting numerical targets for women managers could be successful in raising company awareness of the abilities of women, which was presently not practically used due to gender-based personnel management. Further, young women were found to be inspired to join companies that support women’s empowerment. The results of this study demonstrated that setting numerical targets to increase the number of women managers can be effective in encouraging gender equality in the workplace and can highlight the inherent gender bias in current Japanese personnel management practices