85677-20-9

Upstream product

• 85677-15-2 MOM-allylic carbanion 
• 100-52-7 benzaldehyde 
• 77896-98-1 2-<(Z)-3-(methoxymethoxy)-2-propenyl>-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 62322-45-6 allyl methoxymethyl ether 

Downstream Products

• 145376-17-6 (1R,2R)-1-phenyl-but-3-ene-1,2-diol 
• 19261-14-4 syn-1-phenyl-but-3-en-1,2-diol 

Relevant academic research and scientific papers

An aluminum ate base: Its design, structure, function, and reaction mechanism

An aluminum ate base, i-Bu3Al(TMP)Li, has been designed and developed for regio- and chemoselective direct generation of functionalized aromatic aluminum compounds. Direct alumination followed by electrophilic trapping with I2, Cu/Pd-catalyzed C-C bond formation, or direct oxidation with molecular O2 proved to be a powerful tool for the preparation of 1,2- or 1,2,3-multisubstituted aromatic compounds. This deprotonative alumination using i-Bu3Al(TMP)Li was found to be effective in aliphatic chemistry as well, enabling regio- and chemoselective addition of functionalized allylic ethers and carbamates to aliphatic and aromatic aldehydes. A combined multinuclear NMR spectroscopy, X-ray crystallography, and theoretical study showed that the aluminum ate base is a Li/Al bimetallic complex bridged by the nitrogen atom of TMP and the α-carbon of an i-Bu ligand and that the Li exclusively serves as a recognition point for electronegative functional groups or coordinative solvents. The mechanism of directed ortho alumination reaction of functionalized aromatic compounds has been studied by NMR and in situ FT-IR spectroscopy, X-ray analysis, and DFT calculation. It has been found that the reaction proceeds with facile formation of an initial adduct of the base and aromatic, followed by deprotonative formation of the functionalized aromatic aluminum compound. Deprotonation by the TMP ligand rather than the isobutyl ligand was suggested and reasoned by means of spectroscopic and theoretical study. The remarkable regioselectivity of the ortho alumination reaction was explained by a coordinative approximation effect between the functional groups and the counter Li+ ion, enabling stable initial complex formation and creation of a less strained transition state structure.

ALLYLIC ORGANOMETALLIC WAY TO CONTROL ACYCLIC STEREOCHEMISTRY AND ITS APPLICATION TO THE SYNTHESIS OF CARBOHYDRATES

The Cram/anti-Cram selectivity in the reactions of allylmetals with aldehydes and the erythro/threo selectivity in the reactions of substituted allylic organometallic compounds with other aldehydes can be controlled by the metal (M).Based on both selectiv

Stereoselective Synthesis of Alcohols, XX. - Diastereoselective Addition of γ-Alkoxyallylboronates to Aldehydes

Both the (Z)- and (E)-γ-alkoxysubstituted allylboronates 1 and 3 have been prepared.They add to aldehydes with a diastereoselectivity generally exceeding 90percent to give the syn-(2) and anti-diol derivatives 4, respectively.The structure of one of these adducts has been established by conversion into exo-brevicomin (26).

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.

LIMITED DIASTEREOSELECTIVITY ON ADDITION OF γ-ALKOXY-Z-ALLYLBORONATES TO ALDEHYDES

Addition of Z-γ-alkoxy-allylboronates 2 to aldehydes leads to the homoallylalcohls 3 and 4.Increased steric bulk both on the aldehyde part or the allylboronates causes a decrease in diastereoselectivity.The stereochemistry of the addition is established by novel synthesis of exo-brevicomine.

HETEROSUBSTITUTED ALLYLIC CARBANION BASED STEREOCONTROL. REGIO-AND STEREOSELECTIVE REACTION OF O AND S SUBSTITUTED ALLYLIC CARBANIONS WITH ALDEHYDES

Regio- and diastereoselective reaction of oxygen and sulfur substituted allylic carbanions with aldehydes is described.Either threo or erythro isomer can be obtained predominantly or exclusively by merely choosing an additive.