19549-70-3Relevant articles and documents
Carbonyl reduction with CaH2 and R3SiCl catalyzed by ZnCl2
Tsuhako, Akiko,He, Jing-Qian,Mihara, Mariko,Saino, Naoko,Okamoto, Sentaro
, p. 9120 - 9123 (2008/09/17)
Ketones and aldehydes were effectively reduced to the corresponding alcohols (or their silyl ethers) by the reaction with CaH2 and R3SiCl in the presence of a catalytic amount of ZnCl2. In the absence of the carbonyl substrate, the reagent reduced R3SiCl to the corresponding hydrosilane under mild reaction conditions.
Sequestered alkyllithiums: Why phenyllithium alone is suitable for betaine-ylide generation
Wang, Qian,Deredas, Dariusz,Huynh, Cyril,Schlosser, Manfred
, p. 570 - 574 (2007/10/03)
The key step in the trans-selective modification of the Wittig reaction is the α-lithiation of the lithium bromide coordinated ylide - aldehyde adduct (the so-called "P-betaine"). Only phenyllithium effects this deprotonation rapidly and cleanly. Alkyllithiums (in particular, butyl-, sec-butyl-, and tert-butyllithium) react only sluggishly and incompletely, being tied up in very stable mixed aggregates with the lithium alkoxide part of the betaines.
Ti-TADDOLate-Catalyzed, Highly Enantioselective Addition of Alkyl- and Aryl-Titanium Derivatives to Aldehydes
Weber, Beat,Seebach, Dieter
, p. 7473 - 7484 (2007/10/02)
Toluene-ether or toluene-hexane solutions of aryl and alkyl triisopropoxy titanium reagents (free of Li, Mg, or Zn salts) are prepared from the corresponding Li or Grignard reagents and ClTi(OiPr)3, with careful removal of salts (centrifugation of LiCl or of dioxane*MgX2, and addition of 12-crown-4).The solutions of the organotitanium compounds are combined with one equiv. of an aldehyde and 0.2 equiv. of (R,R)-diisopropoxy-(α,α,α',α'-tetraphenyl-2,2-dimethyl-1,3-dioxolane-4,5-dimethanolato) titanium (Ti-TADDOLate 3) at dry-ice temperature.Warming up to room temperature leads to nucleophilic addition to the (Si)-face of the aldehydes with enantioselectivities as high as 99.5 : 0.5 (products 4-33 in Scheme 4).Functional groups or protecting groups and branching in the Ti-R group and in the aldehyde must be remote from the reacting centers.Aryl groups can be added to aldehydes by this method. - In contrast to all the enantioselective R2Zn additions to aldehydes, in which only one R-group is actually transferred, a twice as economic use is made of the originally employed R-metal reagent in the method described here. - A procedure for multigram preparation of the spiro-Ti-TADDOLate (2) employed for the in situ generation of catalyst (3) is described, and details of the determination of enantiomer ratios (er) by GC and NMR methods are given (Tab. 2, 3).The mechanistic interpretation of Ti-TADDOLate-mediated nucleophilic additions as derived previously (ref.4c) is also compatible with this monometallic variant of the method.