1454-85-9Relevant articles and documents
New strategy for production of primary alcohols from aliphatic olefins by tandem cross-metathesis/hydrogenation
Jia, Ruilong,Zuo, Zhijun,Li, Xu,Liu, Lei,Dong, Jinxiang
, p. 1525 - 1529 (2019/11/11)
Primary alcohols are widely used in industry as solvents and precursors of detergents. The classic methods for hydration of terminal alkenes always produce the Markovnikov products. Herein, we reported a reliable approach to produce primary alcohols from terminal alkenes combining with biomass-derived allyl alcohol by tandem cross-metathesis/hydrogenation. A series of primary alcohol with different chain lengths was successfully produced in high yields (ca. 90percent). Computational studies revealed that self-metathesis and hydrogenation of substrates are accessible but much slower than cross-metathesis. This new methodology represents a unique alternative to primary alcohols from terminal alkenes.
Stabilization of NaBH4 in Methanol Using a Catalytic Amount of NaOMe. Reduction of Esters and Lactones at Room Temperature without Solvent-Induced Loss of Hydride
Prasanth,Joseph, Ebbin,Abhijith,Nair,Ibnusaud, Ibrahim,Raskatov, Jevgenij,Singaram, Bakthan
, p. 1431 - 1440 (2018/02/09)
Rapid reaction of NaBH4 with MeOH precludes its use as a solvent for large-scale ester reductions. We have now learned that a catalytic amount of NaOMe (5 mol %) stabilizes NaBH4 solutions in methanol at 25 °C and permits the use of these solutions for the reduction of esters to alcohols. The generality of this reduction method was demonstrated using 22 esters including esters of naturally occurring chiral γ-butyrolactone containing dicarboxylic acids. This method permits the chemoselective reductions of esters in the presence of cyano and nitro groups and the reductive cyclization of a pyrrolidinedione ester to a fused five-membered furo[2,3-b]pyrrole and a (-)-crispine A analogue in high optical and chemical yields. Lactones, aliphatic esters, aromatic esters containing electron-withdrawing groups, and heteroaryl esters are reduced more rapidly than aryl esters containing electron-donating groups. The 11B NMR spectrum of the NaOMe-stabilized NaBH4 solutions showed a minor quartet due to monomethoxyborohydride (NaBH3OMe) that persisted up to 18 h at 25 °C. We postulate that NaBH3OMe is probably the active reducing agent. In support of this hypothesis, the activation barrier for hydride transfer from BH3(OMe)- onto benzoic acid methyl ester was calculated as 18.3 kcal/mol.
Reductive removal of methoxyacetyl protective group using sodium borohydride
Gadekar, Pradip K.,Hoermann, Maryann,Corbo, Faith,Sharma, Rajiv,Sarveswari,Roychowdhury, Abhijit
, p. 503 - 506 (2014/01/06)
Herein, we have developed a mild and selective reductive deprotection method for the MAc protected alcohols using sodium borohydride. The new deprotection conditions provide a complete orthogonality between O-MAc and other protecting groups such as tert-butyl ester, N-Boc, Fmoc, Cbz, O-TBDMS, N-benzyl, O-benzyl, O-acetyl, N-acetyl, N-MAc, etc. In addition to O-MAc deprotection, this method is also applicable for S-MAc deprotection.