Highly enantioselective carbonyl reduction with borane catalyzed by chiral spiroborate esters derived from chiral 1,2-aminoalcohols

Stepanenko, Viatcheslav; Ortiz-Marciales, Margarita; Correa, Wildeliz; Jesús, Melvin De; Espinosa, Sandraliz; Ortiz, Lymaris

doi:10.1016/j.tetasy.2005.12.005

Cited by 33 publications

(13 citation statements)

References 15 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…8 The reduction of acetophenone in the presence of 7 (5 mol %) affords the product alcohol, 98% ee. 22 The catalyst is similar in enantioselectivity to the B-methyl-CBS oxazaborolidine. 2,4-F 2 C 6 H 3 ; 2-Benzofuryl; 3-and 4-pyridyl a ; 2-MeO-5-pyridyl a ; 2-phenothiazyl a .…”

Section: Brmentioning

confidence: 96%

2-Amino-3-methyl-1,1-diphenyl-1-butanol

Mathre

Shinkai

Zaidlewicz

et al. 2014

Encyclopedia of Reagents for Organic Synthesis

View full text Add to dashboard Cite

Section: Brmentioning

confidence: 96%

2-Amino-3-methyl-1,1-diphenyl-1-butanol

Mathre

Shinkai

Zaidlewicz

et al. 2014

Encyclopedia of Reagents for Organic Synthesis

View full text Add to dashboard Cite

“…Moreover, Huang et al developed a new process using the easily prepared and stable spiroborate ester 1 (Scheme ) as the chiral transfer agent, avoiding the previous catalysts' high cost and air moisture sensitivity. However, in contrast with the growing efforts day by day in designing and developing various kinds of chiral catalysts experimentally [15–29], there have not been any theoretical investigations about the mechanism for the title reaction. As described above, it is very necessary to investigate the mechanisms of the title reaction in detail, which can be helpful to understand how and why the reaction occurs.…”

Section: Introductionmentioning

confidence: 99%

A DFT study of the enantioselective reduction of oxime ethers promoted by chiral spiroborate esters

Qu¹,

Chen²,

Wei³

et al. 2011

Int J of Quantum Chemistry

View full text Add to dashboard Cite

Mechanisms of borane reduction of the (E)-acetophenone O-methyl oxime catalyzed by the easily prepared and stable spiroborate ester 1, derived from diphenylvalinol has been reported for the first time using density functional theory. Two reaction pathways are investigated at the B3LYP/6-31G(d,p) level of theory. The calculated results reveal that this reaction is accomplished via four steps. All the reactants, products, transition states, and intermediates have been optimized at the B3LYP/6-31G (d,p) level. The analysis of these results reveals that one pathway is more energetically favorable than the other, and its associated product is in good agreement with the experimental result. The solvent effect has been further considered at the B3LYP/6-31G(d,p) level in the solvent THF using the PCM model, and the results indicate that it has no great influence on the enantioselectivity of this reduction. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012National Natural Science Foundation of China [20972130, 21072178]; Henan Province (Innovation Specialist Projects

show abstract

“…This is due to the challenges involved in such endeavors and is also due to the applications of homochiral secondary alcohols in organic and medicinal chemistry 3–8. There has been much effort in designing and developing various kinds of chiral catalysts experimentally 9–23.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, Stepanenko et al reported an experimental methodology employing the chiral spiroborate ester such as 1 (Scheme ), as an efficient chiral catalytic source for the borane‐mediated asymmetric reduction of prochiral ketones 23. However, no report of theoretical investigations about the mechanism of title reaction has been found, so it should be useful to give a study in this article.…”

Section: Introductionmentioning

confidence: 99%

A density functional theory study of the enantioselective reduction of prochiral ketones promoted by chiral spiroborate esters

Wei¹,

Tang²,

Zhang³

et al. 2010

Int J of Quantum Chemistry

View full text Add to dashboard Cite

ABSTRACT:Recently, chiral spiroborate ester [(R)-2-((1,3,2-dioxaborolan-2-yloxy)methyl)pyrrolidine] has been experimentally employed as an effective chiral catalyst in the borane-mediated asymmetric reduction of prochiral ketones to produce the corresponding secondary alcohols. In this article, we have theoretically investigated the mechanism of the reduction using density functional theory. The results reveal that this reaction is accomplished via four steps. Fully geometry optimized reactants, products, transition states, and intermediates were obtained at the B3LYP/6-31G (d, p) level. The analysis of these results reveals one pathway that is more energetically favorable, and its associated geometries correlate well with the final products of the reaction. The further calculations show that the solvent effect of THF has no great influence on enantioselectivity of this reduction.

show abstract

Highly enantioselective carbonyl reduction with borane catalyzed by chiral spiroborate esters derived from chiral 1,2-aminoalcohols

Cited by 33 publications

References 15 publications

2-Amino-3-methyl-1,1-diphenyl-1-butanol

2-Amino-3-methyl-1,1-diphenyl-1-butanol

A DFT study of the enantioselective reduction of oxime ethers promoted by chiral spiroborate esters

A density functional theory study of the enantioselective reduction of prochiral ketones promoted by chiral spiroborate esters

Contact Info

Product

Resources

About