Generation of Highly Enantioselective Catalysts from the Pseudoenatiomeric Assembly of BINOL, F8BINOL, and Ti(OiPr)4

Pandiaraju, Subramanian; Chen, Gang; Lough, and Alan J.; Yudin, Andrei K.

doi:10.1021/ja0039942

Cited by 74 publications

(37 citation statements)

References 25 publications

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“…Yudin and co-workers [217] examined the use of the Ti catalyst prepared from a mixture of pseudo-enantiomeric binol and F 8 binol (252) in the same reaction [Eq. (80)].…”

Section: Reviews 486 Wwwangewandteorgmentioning

confidence: 99%

Nonlinear Effects in Asymmetric Catalysis

Satyanarayana¹,

Abraham²,

Kagan³

2008

Angew Chem Int Ed

500

273

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There is a need for the preparation of enantiomerically pure compounds for various applications. An efficient approach to achieve this goal is asymmetric catalysis. The chiral catalyst is usually prepared from a chiral auxiliary, which itself is derived from a natural product or by resolution of a racemic precursor. The use of non-enantiopure chiral auxiliaries in asymmetric catalysis seems unattractive to preparative chemists, since the anticipated enantiomeric excess (ee) of the reaction product should be proportional to the ee value of the chiral auxiliary (linearity). In fact, some deviation from linearity may arise. Such nonlinear effects can be rich in mechanistic information and can be synthetically useful (asymmetric amplification). This Review documents the advances made during the last decade in the use of nonlinear effects in the area of organometallic and organic catalysis.

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“…Yudin and co-workers [217] examined the use of the Ti catalyst prepared from a mixture of pseudo-enantiomeric binol and F 8 binol (252) in the same reaction [Eq. (80)].…”

Section: Reviews 486 Wwwangewandteorgmentioning

confidence: 99%

Nonlinear Effects in Asymmetric Catalysis

Satyanarayana¹,

Abraham²,

Kagan³

2008

Angew Chem Int Ed

500

273

View full text Add to dashboard Cite

show abstract

“…We reasoned that if one of the enantiomers of BINOL is replaced by its fluorinated analogue, a "pseudo-maso" aggregate might be formed for similar geometrical reasons as in the BINOL case. Homochiral FgBINOL was thus investigated in titanium-catalyzed asymmetric glyoxylate-ene process using literature conditions (28). The results showed that the same sense of asymmetric induction was observed for both Ti/fS;-F 8 BINOL and Ti/(S>BINOL catalysts, whereas, initial rate studies indicated that the catalyst derived from FgBINOL was approximately 4 times slower than the one derived from BINOL.…”

Section: Glyoxylate-ene Reactionmentioning

confidence: 92%

Polyfluorinated Binaphthol Ligands in Asymmetric Catalysis

Chen

Yudin

2005

ACS Symposium Series

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“…Water was added dropwise keeping the temperature at 4 8C until all excess POCl 3 was quenched. The resulting mixture was extracted with dichloromethane and purified by flash column chromatography ( 10,131.65,129.04,128.79,127.18,122.36,121.66,106.26,6,7, To a solution of 4 (927 mg, 3 mmol) in dichloromethane (15 ml) was added BBr 3 (2.25 g, 9 mmol) at room temperature under nitrogen atmosphere. The reaction was stirred for 15 h at room temperature, then cooled to 0 8C and quenched by slow addition of water.…”

Section: -Methoxy-naphthalene-1-sulfonyl Chloride (20)mentioning

confidence: 99%

“…We recently, published the synthesis and catalytic applications of polyfluorinated BINOL ligands such as F 8 BINOL (3), an electronic isostere of BINOL [8]. In terms of catalytic applications, we explored the sulfoxidation [9] as well as the glyoxylateene reaction [10]. It was found that the (R)-F 8 BINOL-Ti system catalyzed the sulfoxidation reaction with higher enantioselectivity (89% in CH 2 Cl 2 ) than the (R)-BINOL-Ti system (7% in CH 2 Cl 2 and 22% in CCl 4 ) at 0.05 M concentration.…”

Section: Introductionmentioning

confidence: 99%