Multinuclear Cu-Catalysts Based on SPINOL-PHOS in Asymmetric Conjugate Addition of Organozinc Reagents

Endo, Kohei; Hamada, Daisuke; Yakeishi, Sayuri; Ogawa, Mika; Shibata, Takanori

doi:10.1021/ol300748d

Cited by 43 publications

(13 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Shibata and co-workers developed a method of using Cu/Zn complex catalyzed alkylation at the α,β-unsaturated position (compound 34 ). S - 34 was obtained by ( S )-6,6′-SPINOL-PHOS ( 35 ), while R - 34 was prepared with ( S )-4,4′-SPINOL-PHOS ( 36 ), both of which had over 90% ee . The R -isomer was also synthesized using Cu(OTf) 2 and aminohydroxyphosphine ( 37 ), with 98% ee .…”

Section: Chemical Reactions Related To Michael Acceptorsmentioning

confidence: 99%

Chalcone: A Privileged Structure in Medicinal Chemistry

et al. 2017

View full text Add to dashboard Cite

Privileged structures have been widely used as an effective template in medicinal chemistry for drug discovery. Chalcone is a common simple scaffold found in many naturally occurring compounds. Many chalcone derivatives have also been prepared due to their convenient synthesis. These natural products and synthetic compounds have shown numerous interesting biological activities with clinical potentials against various diseases. This review aims to highlight the recent evidence of chalcone as a privileged scaffold in medicinal chemistry. Multiple aspects of chalcone will be summarized herein, including the isolation of novel chalcone derivatives, the development of new synthetic methodologies, the evaluation of their biological properties, and the exploration of the mechanisms of action as well as target identification. This review is expected to be a comprehensive, authoritative, and critical review of the chalcone template to the chemistry community.

show abstract

Section: Chemical Reactions Related To Michael Acceptorsmentioning

confidence: 99%

Chalcone: A Privileged Structure in Medicinal Chemistry

et al. 2017

View full text Add to dashboard Cite

show abstract

“…reported the reaction using acyclic unsaturated ketoesters gave acyclic γ‐ketoesters (Table 1, entries 1–9). BINOL derivatives B m P and BP or the SPINOL derivative SP gave opposite major enantiomers, respectively 11c,d. The screening of Cu salt showed that the use of Cu(OAc) 2 gave the product in better yield with excellent ee values (entries 10–14).…”

Section: Methodsmentioning

confidence: 99%

Highly Chemo‐, Enantio‐, and Regioselective Synthesis of α,α‐Disubstituted Furanones by Cu‐Catalyzed Conjugate Addition

Endo¹,

Yakeishi²,

Takayama³

et al. 2014

Chemistry A European J

Self Cite

View full text Add to dashboard Cite

A highly chemo-, enantio-, and regioselective synthesis of furanones bearing an α,α-disubstituted quaternary stereogenic center is reported. The Cu-catalyzed enantioselective conjugate addition of organoaluminum reagents to unsaturated ketoesters at room temperature and subsequent lactonization took place. Synthetic transformations of furanones represent facile approaches to various cyclic or acyclic compounds bearing a quaternary stereogenic center.

show abstract

“…22 In contrast, the use of SPINOL derivative SP as a ligand gave the opposite major enantiomers selectively (Scheme 20). 23 Ligands bearing phosphorous moieties at the ortho-position to a hydroxyl group gave the (S )-product as a major enantiomer and ligands bearing phosphorous moieties at the para-position to a hydroxyl group gave the (R)-product as a major enantiomer. The BINAM-based ligands BNmP unexpectedly gave the desired products as the opposite major enantiomers compared to those using BINOLbased ligands (Scheme 21).…”

Section: Bpinmentioning

confidence: 99%

Development of Neighboring Electrophilic Activation of Active Center in Catalytic Reactions via Organometallic Intermediates

Endo

2017

Bulletin of the Chemical Society of Japan

Self Cite

View full text Add to dashboard Cite

Strategies for electrophilic activation by neighboring atoms should contribute to the development of novel catalytic performance in organic reactions. Neighboring electron-withdrawing Lewis acidic atoms can change the character of molecular catalysts, which might be more electrophilic toward inactive electron-rich molecules. In this context, the development of carbene intermediates, diborylmethane derivatives, and multinuclear catalysts has realized efficient transformations. The use of cyclopropenes can generate electrophilic carbenoid intermediates in the presence of a Ag-catalyst, the reaction of which with an organozinc reagent gives allylzinc intermediates. The subsequent allylation reaction of other electrophiles takes place in situ as a 3-components coupling reaction. The novel reactivity of diborylmethane derivatives shows the generation of borate intermediates under ambient conditions, which can take part in the SuzukiMiyaura cross-coupling reaction. The mono-coupling reaction occurs exclusively without di-coupling reaction to give alkylboronates. The stereoselective synthesis of tetrasubstituted alkenylboronates was successful via the deprotonation of diborylalkanes, subsequent nucleophilic attack to ketones, and syn-elimination. The development of multinuclear catalysts using phosphorous ligands bearing protic moieties has realized efficient stereoselective 1,4-addition reaction of organozinc and organoaluminum reagents, where the creation of chiral quaternary stereogenic centers using acyclic enones is notable.

show abstract

Multinuclear Cu-Catalysts Based on SPINOL-PHOS in Asymmetric Conjugate Addition of Organozinc Reagents

Cited by 43 publications

References 18 publications

Chalcone: A Privileged Structure in Medicinal Chemistry

Chalcone: A Privileged Structure in Medicinal Chemistry

Highly Chemo‐, Enantio‐, and Regioselective Synthesis of α,α‐Disubstituted Furanones by Cu‐Catalyzed Conjugate Addition

Development of Neighboring Electrophilic Activation of Active Center in Catalytic Reactions via Organometallic Intermediates

Contact Info

Product

Resources

About