85125-31-1

Upstream product

• 119703-54-7 C₆H₁₃Si^(1-) 
• 100-52-7 benzaldehyde 
• 79448-25-2 (3-(trimethylsilyl)allyl)lithium 
• 762-72-1 allyl-trimethyl-silane 
• 85682-98-0 C₁₈H₄₁O₄SiTi^(1-)*Li⁽¹⁺⁾ 
• 94397-40-7 (1-bromoallyl)trimethylsilane 

Downstream Products

• 31915-94-3 (Z)-1-Phenylbuta-1,3-diene 
• 16939-57-4 (E)-buta-1,3-dienylbenzene 

Relevant academic research and scientific papers

Regio- and stereo-selective reactions of trimethylsilyl-substituted allyl-chromium reagents with aldehydes

The use of the title compounds in the syntheses of anti-β-hydroxysilanes (3) and vinylsilanes (13-14) is described.

THE INFLUENCE OF (ORGANO)METALLICS "METAL-TUNING" ON STEREO- AND REGIO-CHEMICAL CONVERGENCE IN REACTIONS OF ALLYLIC CARBANIONS WITH ALDEHYDES

Although the reaction of heterosubstituted allylic carbanions (2) with aldehydes generally produces a mixture of the γ- and α-adducts (4 and 3), syn-3 and anti-3 can be prepared either exclusively or predominantly by the proper choice of the organometallic compound added.

Stereoselective Addition of Organotitanium Reagents to Carbonyl Compounds

Titanation of alkyllithium or -magnesium compounds using ClTi(OR)3 results in reagents which show markedly increased diastereofacial selectivity (80 - 90percent) in reactions with α-chiral aldehydes or ketones.Titanation is also the method of choice in Grignard-type additions to substituted cyclohexanones; CH3Ti(OCHMe2)3 (6a) adds predominantly from the equatorial direction, while allyltitanium reagents 11b and 12 show axial preference.Crotyltitanium compounds react with carbonyl compounds to afford primarily adducts having anti-configuration, a process which is of particular value in case of ketones (anti/syn ratios up to 99:1).Titanation of (trimethylsilyl)allyllithium (48) with Ti(OCHMe2)4 reverses regioselectivity in reactions with aldehydes and ketones, β-hydroxy silanes 50 being the only observed products.These have anti-configuration and can be converted either into Z- or E-dienes using the Peterson elimination under basic or acidic conditions, respectively.

Regiochemical Convergence in the Reaction of Heterosubstituted Allylic Carbanions via Allylic Aluminum and Boron "Ate" Complexes

The regiochemistry in reactions of heterosubstituted allylic carbanions (1) is highly controlled via allylic aluminum or boron "ate" complexes which direct both carbonyl compounds and reactive halides to the α-position with high regioselectivity.For example, carbonyl compounds react with the oxygen- (3), sulfur- (12), selenium- (20), and silicon- (25) substituted allylic carbanions at the α-position via the ate complexes.Although the reactions of the ate complexes (2) with aldehydes generally produce a mixture of erythro and threo isomers, the aluminum ate comlex of 3b gives the erythro isomer (5) with very high stereoselectivity.This procedure is applied to the stereoselective synthesis of exo-brevicomin (9).With allylic halides, the oxygen- (3a) and sulfur- (12) substituted allylic carbanions again react at the α-position via the ate complexes.However, the coupling mode is entirely different; the α-α' coupling product (10) is obtained from 3a, while the α-γ' coupling product (15) is produced from 12.

CONTROLLED REVERSAL OF CHEMOSELECTIVITY IN REACTIONS OF ALLYLTITANIUM ATE COMPLEXES WITH CARBONYL COMPOUNDS

Allyltitanium ate complexes react either aldehyde- or ketone-selectively, depending upon the nature of the ligands at titanium.

A STEREO- AND REGIO-SPECIFIC ADDITION OF ν3-TRIMETHYLSILYLALLYLTITANIUM COMPOUND WITH ALDEHYDES. A FACILE AND STEREOCONTROLLED SYNTHESIS OF E- AND Z-TERMINAL DIENES

ν3-Trimethylsilylallyltitanium compound, (ν5-C5H5)2Ti(ν3-1-trimethylsilylallyl), reacts with aldehydes to give (+/-)-(R,S)-3-trimethylsilyl-4-hydroxy-1-alkenes in excellent yields, which can be deoxysilylated to either E- or Z-1,3-dienes.

Stereocontrol using a Heterosubstituted Allylic Carbanion. Regio- and Stereo-selective Reactions of Trimethylsilyl Allylic Carbanions with Aldehydes

Regio- and stereo-selective coupling between trimethylsilyl allyl carbanions and aldehydes is achieved in the presence of an additive, 'M'; use of R2BCl or EtAlCl2 as the additive gives the threo isomer (3) predominantly, while use of Bu3SnCl-BF3 affords the erythro isomer exclusively.

A STEREOCONTROLLED SYNTHESIS OF Z AND E TERMINAL DIENES FROM PINACOL E-1-TRIMETHYLSILYL-1-PROPENE-3-BORONATE

Pinacol E-1-trimethylsilyl-1-propene-3-boronate reacts with aldehydes to form (+)-(R*, S*)-3-trimethylsilyl-4-hydroxy-1-alkenes, which can be deoxysilylated stereoselectively to either 98percent Z or 99percent E 1,3-dienes, including the separate components of the red bollworm moth pheromone.