A selective reduction method of an electronically deficient imine in the presence of ketone was developed by employing Et(2)Zn and 5 mol % of Ni(acac)(2). The method was applied in the reduction of S(S)-tert-butanesulfinyl ketimines 1 to afford amines 2 in 23-92% yields and 73:27 to 98:2 diastereoselectivities. A plausible mechanism was proposed on the basis of an NMR study.

Self-condensation of tert-butanesulfinimine 5 was realized in the presence of tetrabutylammonium fluoride to afford a,bunsaturated sulfinimine 8 in moderate to high yields with high geometric selectivities. The synthesized a,b-unsaturated sulfinimine 8 was demonstrated to be a versatile intermediate for the syntheses of enal 4 and chiral allyl amine 11.It is well known that the high reactivity of aldehydes often leads to complicated product mixtures due to self-condensation reactions. To resolve this problem, 1 an aldehyde was usually transformed to the stable enamine 1 and then condensed with aldehyde 2 to give enal 4. Although the imine functional group of sulfinimine 5 2 is susceptible to attack by a nucleophile such as organometallic reagent 3 and enolate, 4 the a-proton of sulfinimine 5 can be deprotonated upon treatment with a base to form an azaenolate 6, 5 which may undergo an aza-Mannich type self-condensation to afford b-sulfinamido sulfinimine 7 (Scheme 1). Scheme 1We recently reported a simple and highly efficient method to prepare tert-butanesulfinimine 5 and its applications in Ni(acac) 2 -catalyzed diethylzinc reduction and synthesis of taxol side chain. 6 In order to expand the application scope of tert-butanesulfinimine 5 in organic synthesis, we further explored the possibility that sulfinimine 5 can act as an equivalent of enamine to accomplish an aza-Mannich type of self-condensation. In this letter, we disclose the preliminary result that self-condensation of sulfinimine 5 leads to the formation of a,b-unsaturated sulfinimine 8 by using tetrabutylammonium fluoride (TBAF) as a base. Scheme 2 Self-condensation of sulfinimine 5 promoted by TBAF Initially, we screened different bases in toluene for the self-condensation reaction of racemic sulfinimine 5a (R = hexyl) at room temperature. Among the tested bases (1.2 equiv) such as triethylamine, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), TBAF, tetrabutylammonium chloride (TBAC), tetrabutylammonium bromide (TBAB), tetrabutylammonium iodide (TBAI), tetrabutylammonium triphenyldifluorosilicate (TBAT), and cesium fluoride, only TBAF successfully promoted the self-condensation of 5a within one hour to afford a,b-unsaturated sulfinimine 8a 7 in 37% yield (E/Z = 23:1) and tert-butanesulfinamide 9 in 32% yield. Isolation of 8a instead of b-sulfinamido sulfinimine 7a indicated that 7a was not stable under the reaction conditions, and that b-elimination of tert-butanesulfinamide moiety in 7a occurred during the reaction (Scheme 2). Encouraged by the above results, we then studied the effects of different solvents on the condensation reaction of 5a in the presence of 1.2 equivalents of TBAF at room temperature. As

The present study aimed to determine the effect of recombinant DNA vaccine-based human epidermal growth factor receptor-2 (HER2) and Interleukin 12 (IL-12) on the development of colonic carcinoma in mice and the potential immune mechanisms involved. Recombinant plasmids pVAX1-HER2, pVAX1-IL-12 and pVAX1-HER2-IL-12 were constructed, and injected into female mice intramuscularly (i.m.) followed by an electric pulse. The humoral and cellular immune responses after immunization were examined by enzyme linked immunosorbent assay (ELISA) and enzyme-linked immunospot assay (ELISPOT), respectively. To evaluate the anti-tumor efficacy of the plasmids, a mouse model with a HER2-expressing tumor was designed. Mice vaccinated with the HER2-IL-12 plasmid generated the strongest inhibition efficacy on the growth of HER2-expressing tumors and prolonged mouse survival. These observations emphasized the potential of IL-12 as an adjuvant for DNA vaccines and of vaccines based on HER2 and IL-12 as a promising treatment for colonic carcinoma.

In the title compound, C21H23NO2, the dihedral angle between the indole ring system and the benzyl ring is 75.92 (9)°. The crystal packing is controlled by C—H⋯O and C—H⋯π inter­actions.

Sulfinic acids P 0420Aza-Mannich Condensation of Sulfinimine Promoted by Tetrabutylammonium Fluoride: Synthesis of α,β-Unsaturated Sulfinimine. -It is discovered that tert-butylsulfimine can act as an equivalent of enamines for the preparation of α-,β-unsaturated sulfimine through an aza-Michael-type self condensation. Further transformations are investigated. -(BIAN, X.; ZHANG, D.; HUANG