1246895-92-0

Upstream product

• 7228-47-9 2-(2-naphthyl)ethanol 
• 100-51-6 benzyl alcohol 
• 90878-19-6 phenethylmagnesium chloride 
• 66-99-9 β-naphthaldehyde 
• 3277-89-2 phenethylmagnesium bromide 

Relevant academic research and scientific papers

Stereospecific Stille Cross-Couplings Using Mn(II)Cl2

Cross-coupling reactions are a staple in organic synthesis, especially for C-C bond formation with sp- and sp2-carbon electrophiles. In recent years, the range of accessible C-C bonds has been extended to stereogenic centers which expedites access to greater molecular complexity. However, these reactions predominantly depend upon late transition metal (LTM) catalysts whose cost, toxicity, and/or environmental impact have come under increasing scrutiny and governmental regulation. Here, we report Mn(II)Cl2 complexes alone, or with assistance from copper, catalyze the stereospecific cross-coupling of α-alkoxyalkylstannanes with organic electrophiles with complete retention of configuration.

Room-Temperature Guerbet Reaction with Unprecedented Catalytic Efficiency and Enantioselectivity

We report herein an unprecedented highly efficient Guerbet-type reaction at room temperature (catalytic TON up to >6000). This β-alkylation of secondary methyl carbinols with primary alcohols has significant advantage of delivering higher-order secondary alcohols in an economical, redox-neutral fashion. In addition, the first enantioselective Guerbet reaction has also been achieved using a commercially available chiral ruthenium complex to deliver secondary alcohols with moderate yield and up to 92 % ee. In both reactions, the use of a traceless ketone promoter proved to be beneficial for the catalytic efficiency.

Catalytic highly enantioselective alkylation of aldehydes with deactivated grignard reagents and synthesis of bioactive intermediate secondary arylpropanols

Because of the high reactivity of Grignard reagents, a direct, highly enantioselective Grignard reaction with aldehydes has rarely been disclosed. In this report, Grignard reagents were introduced with bis[2-(N,N′- dimethylamino)ethyl] ether (BDMAEE) to effectively deactivate their reactivity; thus, a highly enantioselective alkylation of aldehydes with Grignard reagents resulted from catalysis by (S)-BINOL-Ti(OiPr)2. It is thought that BDMAEE chelates the in situ generated salts MgBr2 from a Schlenk equilibrium of RMgBr and Mg(OiPr)Br from transmetalation of RMgBr with Ti(OiPr)4. The Mg salts can actively promote the undesired background reaction to give the racemate. The chelation definitely inhibits the catalytic activity of the Mg salts, suppresses the unwanted background reaction, and enables the highly enantioselective addition catalyzed by (S)-BINOL-Ti(OiPr)2. Consequently, the Mg salt byproducts were not removed, less Ti(OiPr)4 than RMgBr was used, and extremely low temperature was avoided in this catalytic asymmetric reaction in comparison with the research disclosed before. Various alkyl Grignard reagents were investigated in the asymmetric addition, and iBuMgBr resulted in the highest enantioselectivity, >99%. Furthermore, important intermediate secondary arylpropanols for chiral drug synthesis were effectively synthesized with high enantioselectivity, up to 97%, in one step.