Diastereoselective addition of silyl- and stannyl metals to γ-alkoxy-alkylidene malonates

Krief, Alain; Dumont, Willy; Baillieul, Diane

doi:10.1016/j.tetlet.2005.09.063

Cited by 6 publications

(1 citation statement)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[273][274] The obtained triorganosilylzincates were used in various reactions resulting in moderate to good yields and it was found to be superior to silylcuprates in most of the reactions. 155,227,250,[272][273][274][275][276][277][278] Scheme 84 Synthesis of mixed triorganosilylzincate by Oshima and Fleming…”

Section: Scheme 83 Synthesis Of Triorganosilylzincatementioning

confidence: 99%

Preparations of Silyl Anions

Rasappan,

Pulikkottil,

Balakrishnan

et al. 2023

Synthesis

View full text Add to dashboard Cite

This review is collective writing on synthetic procedures for the synthesis of different silyl nucleophiles which are valuable reagents for chemists, particularly in the field of organic synthesis and organometallic chemistry. We have described the preparations of silyl nucleophiles of lithium, sodium, potassium, rubidium, and caesium from group I metals. We have also focused on silyl anions of beryllium, magnesium, calcium, strontium, and barium from group II metals. We included synthetic procedures for silyl anions of zirconium, hafnium, cadmium, and zinc. The synthesis of group XIII silyl anions of boron and aluminium is also highlighted in this short review.

show abstract

Section: Scheme 83 Synthesis Of Triorganosilylzincatementioning

confidence: 99%

Preparations of Silyl Anions

Rasappan,

Pulikkottil,

Balakrishnan

et al. 2023

Synthesis

View full text Add to dashboard Cite

show abstract

Dilithium Cyanobis(dimethylphenylsilyl)cuprate

Marino

Holub

Fleming

2008

Encyclopedia of Reagents for Organic Synthesis

View full text Add to dashboard Cite

The Krapcho Dealkoxycarbonylation Reaction of Esters with α‐Electron‐Withdrawing Substituents

Krapcho

Ciganek

2013

Organic Reactions

View full text Add to dashboard Cite

The Krapcho reaction involves esters with α‐electron‐withdrawing substituents such as malonates, β‐keto esters, and α‐cyano esters, which undergo dealkoxycarbonylation on being heated in polar aprotic solvents (such as DMSO, DMF, or HMPT) in the presence of water, or in polar aprotic solvents with water in the presence of added salts (such as NaCN, NaCl, LiCl, LiI, or MgCl 2 ). This procedure avoids the use of strongly aqueous acidic and alkaline conditions and tolerates many functional and protecting groups. The chapter presents the mechanistic aspects of this procedure, which include reaction parameters such as solvents, salts, other additives, and the use of microwave irradiation. The diastereoselectivity of protonation of the enolate intermediate leading to the dealkoxycarbonylated products is discussed. Trapping of the intermediate enolate by electrophiles other than a proton is illustrated. Potential side reactions and same‐pot subsequent reactions of substrates are discussed along with functional‐group compatibility for halogens and nitrogen, oxygen, sulfur, selenium, and carbon functional groups. Several examples of applications of this methodology for the synthesis of natural products along with experimental conditions and procedures are presented. Closely related methods are discussed in the Comparison with Other Methods section. The tables, which consist of 371 pages, are grouped according to substrate structure. Selective entries for other methods (excluding classical aqueous acidic or basic methods) are included in the tabular survey for comparative purposes.

show abstract

Diastereoselective addition of silyl- and stannyl metals to γ-alkoxy-alkylidene malonates

Cited by 6 publications

References 20 publications

Preparations of Silyl Anions

Preparations of Silyl Anions

Dilithium Cyanobis(dimethylphenylsilyl)cuprate

The Krapcho Dealkoxycarbonylation Reaction of Esters with α‐Electron‐Withdrawing Substituents

Contact Info

Product

Resources

About