123290-33-5Relevant articles and documents
Nucleophilic Reactivity of Zinc and Copper Carbenoids. 2
Knochel, Paul,Chou, Tso-Sheng,Chen, Huai Gu,Yeh, Ming Chang P.,Rozema, Michael J.
, p. 5202 - 5204 (1989)
The rectivity of the new zinc and copper carbenoids PivOCH2Cu(CN)ZnI (4) and ICH2Cu*ZnI2 (5) toward various electrophiles has been investigated.Of special interest is the direct and highly stereoselective conversion of allylic bromides to the corresponding homoallylic iodides by using the reagent ICH2Cu*ZnI2
Preparation and Reactivity of Highly Functionalized Organometallics at the α Position of Oxygen or Nitrogen
Knochel, Paul,Chou, Tso-Sheng,Jubert, Carole,Rajagopal, Duddu
, p. 588 - 599 (2007/10/02)
α-Halogenoalkyl carboxylates (FG-R1CH(X)(OCOR2); FG = COOR, CN, SR; X = I, Br) were readily prepared by the addition of an acid chloride or bromide (R2COX; X = Br or Cl) to an aldehyde (FG-RCHO) in the presence of a catalytic amount of ZnCl2.They insert efficiently zinc dust in THF-DMSO (X = Br, 8 - 10 deg C, 6 - 10 h) affording the corresponding zinc organometallics at the α position to oxygen FG-RCH(ZnBr)(OAc).After the addition of the THF-soluble copper salt CuCN*2LiCl, the corresponding copper reagents FG-RCH(Cu(CN)ZnBr)(OAc) are formed and reacted with variousclasses of electrophiles such as acid chlorides, aldehydes, enones, allylic and alkynyl halides, activated alkynes, nitro olefins and alkylidenemalonates providing polyfunctional molecules in excellent yields.Similarly, zinc organometallics at the α position to the nitrogen of cyclic imides were prepared by the zinc insertion to cyclic α-chloromethyl (or α-chloroethyl) imides.After their transmetalation to the corresponding copper organometallic ((R1CO)2NCH(R)(Cu(CN)ZnCl); R = Me or H), they were reacted with allylic and alkynyl halides and ethyl propiolate affording polyfunctional imides.The reaction of cyclic N-(chloromethyl)imides with aldehydes in the presence of chromium(II) chloride in THF furnishes protected amino alcohols in 36 - 95percent yield.
