Endo entry to the nortricyclyl-norbornenyl cation system: stereochemistry in the fragmentation of endo-5-norbornenyl-2-oxychlorocarbene

Fragmentation of (S)-endo-5-norbornenyl-2-oxychlorocarbene [(S)-8] in cyclohexane-d12 gives approximately 20% (S)-endo-2-chloro-5-norbornene [(S)-7] with approximately 50% ee, 65-70% (R)-exo-2-chloro-5-norbornene [(R)-4] with >95% ee, and approximately 12% (R)-3-nortricyclyl chloride [(R)-5] with approximately 22% ee. (Analogous stereochemical results were also obtained starting with the enantiomeric carbene (R)-8.) The (S)-8 to (S)-7 and (S)-8 to (R)-4 conversions are ascribed mainly to retention and inversion S(N)i transition states, respectively. These have been located by computational methods and are nearly isoenergetic. In more polar solvents (CDCl3 and CD3CN), the fragmentation of (S)-8 increasingly occurs via competitive ion pair pathways in which steroselectivity is diminished, and escape to the norbornenyl-nortricyclyl cation directs the products away from endo-2-chloro-5-norbornene toward exo-chloride 4 and nortricyclyl chloride 5.     

First organocatalyzed asymmetric Michael addition of aldehydes to vinyl sulfones

[reaction: see text] The first asymmetric direct Michael addition of aldehydes to vinyl sulfones catalyzed by N-iPr-2,2'-bipyrrolidine is described. 1,4-Adducts are obtained in good yields and enantioselectivities. The determination of absolute configuration allowed us to postulate a Si,Si transition state model, as shown previously for nitroolefins.     

萨满医术:北方民族精神医学

治病是北方少数民族萨满的主要职能之一。在信仰萨满教的民族中萨满往往充当民间医生的角色。萨满医术是一种精神医术和心灵医术。萨满主要是治心因性的精神疾病,其主要治疗手段也是一种心理治疗。在萨满医术中包含着现代精神医学中使用的一些治疗方法和治愈机制。萨满的精神医术之本质在于通过各种方式使患者的心理得到平衡,与此同时让患者振作起来,对自己的病情持乐观的态度,确立战胜病魔的信心。萨满精神医术就是一种典型的宗教性心理——生理调控术。对萨满医术,应从心理人类学、医学人类学、宗教人类学等多种角度进行研究,这样才能够得出比较全面而相对正确的结论。