Stereochemistry of the reactions of substituted allylboronates with chiral aldehydes.  Factors influencing aldehyde diastereofacial selectivity

Roush, William; Adam, Michael A.; Walts, Alan E.; Harris, David

doi:10.1021/ja00272a043

Cited by 171 publications

(43 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[36] This sequence affords the homoallylic alcohols as a 4:1 mixture of diastereomers favoring the desired product. A number of other crotylmetal reagents were surveyed, including the Hiyama (E)-crotylchromium, [37] RoushЈs (E)-crotylpinacol borane, [38] and RoushЈs (E)-crotyltartarate borane. [39] However, each of these reagents gave lower selectivities (dr ϭ 2:1 Ǟ 3:1 anti/ syn).…”

Section: Omura؊smith Synthesismentioning

confidence: 99%

Syntheses and Biological Evaluation of (+)-Lactacystin and Analogs

et al. 2000

View full text Add to dashboard Cite

Since its isolation in 1991, (+)-lactacystin (1) has attracted considerable attention among leading synthesis laboratories due to its highly selective and potent inhibition of the 20S proteasome. The syntheses of this molecule described herein demonstrate several important strategies in the area of acyclic stereocontrol including the use of chiral metal enolate and chiral allylmetal-based bond construction methods. Figure 1) is a secondary metabolite derived from a streptomyces bacterial strain (OM-6519) [a] with the area of organic synthesis. His research group is engaged in the development of new reaction methodology concerned with acyclic stereocontrol as well as the application of these methods to the asymmetric synthesis of natural products and complex organic molecules. Biological Activity of Lactacystin Adam J. Morgan was born in 1978 in Phoenix, AZ. He is currently a senior at Boston University working toward a B. A. degree in chemistrywhere he is engaged in undergraduate research in the laboratories of Professor James S. Panek. For the past two summers, he has been the recipient of a Pfizer PREPARE fellowship. His research efforts include the asymmetric syntheses of natural products containing α-amino-β-hydroxyacid functionalities. Upon graduation, he plans on pursuing a career in the pharmaceutical industry.MICROREVIEWS: This feature introduces the readers to the authors' research through a concise overview of the selected topic. Reference to important work from others in the field is included.

show abstract

Section: Omura؊smith Synthesismentioning

confidence: 99%

Syntheses and Biological Evaluation of (+)-Lactacystin and Analogs

et al. 2000

View full text Add to dashboard Cite

show abstract

“…All organic solvents used were commercially available dry solvents, which were distilled appropriately under an argon atmosphere and stored over molecular sieves prior in an Ar box. Allyl boronate 3, [26] a-methylallyl boronate 9, [27] (Z)-crotyl boronate 10, [26] methallyl boronate 11, [28] a-(trimethylsilyl)allyl boronate 12, [29] allenyl boronate 17,…”

Section: Methodsmentioning

confidence: 99%

Palladium(0) versus Nickel(0) Catalysis in Selective Functional‐Group‐Tolerant sp³–sp³ Carbon–Carbon Bond Formations

Flegeau

Schneider

Kobayashi

2009

Chemistry A European J

View full text Add to dashboard Cite

We have uncovered Pd(0)-catalyzed intermolecular nonsymmetrical Suzuki-Miyaura-type sp(3)-sp(3) C-C bond formations between allyl carbonates and nontoxic allyl, allenyl, or propargyl boronates. This report represents the first use of these types of boronic esters in this particular context. The present transformations proceeded with high selectivity under remarkably mild conditions, and various functional groups including an aldehyde function proved to be compatible. In addition, several boronates were found to display very unusual reactivity patterns; the higher reactivity of boron as apposed to silicon was clearly demonstrated as well. Finally, the inherent problem of beta-hydride elimination associated with intermediary allyl-Pd species was addressed by employing a commercially available Ni(0) catalyst.

show abstract

“…The observed stereoselectivity can be explained by the favorable attack of carbanion from si-face of the sugar aldehyde leading to 'S' isomer as major product at the newly created center according to Felkin-Ahn model [44] by a non-chelation protocol. The observed stereoselectivity can be explained by the favorable attack of carbanion from si-face of the sugar aldehyde leading to 'S' isomer as major product at the newly created center according to Felkin-Ahn model [44] by a non-chelation protocol.…”

Section: B) Asymmetric Baylis-hillman Reaction Using Chiral Electrophmentioning

confidence: 99%

Asymmetric Baylis-Hillman Reaction: Use of Novel Chiral Aldehydes as Electrophiles, Chiral Base Catalysts and Auxilliaries&#

Krishna¹,

Sharma

2006

MROC

View full text Add to dashboard Cite

The present review highlights our recent research findings in the field of asymmetric Baylis-Hillman reaction. In particular, it elaborates on the following efficient aids: 1) utilization of sugar-derived acrylates as chiral auxiliary for diastereoselective Baylis-Hillman reaction; 2) use of novel chiral electrophiles such as sugar-derived aldehydes and chiral 2,3-epoxy aldehydes for the diastereoselective Baylis-Hillman reaction to obtain valuable chiral adducts; 3) a novel prolinol derivative promoted enantioselective Baylis-Hillman reaction and 4) intramolecular Baylis-Hillman reaction wherein both the aldehyde and acrylate component are part structure of the same molecular framework to afford high de's. This review also covers the related research work from other groups on asymmetric Baylis-Hillman reaction.

show abstract

Stereochemistry of the reactions of substituted allylboronates with chiral aldehydes. Factors influencing aldehyde diastereofacial selectivity

Cited by 171 publications

References 0 publications

Syntheses and Biological Evaluation of (+)-Lactacystin and Analogs

Syntheses and Biological Evaluation of (+)-Lactacystin and Analogs

Palladium(0) versus Nickel(0) Catalysis in Selective Functional‐Group‐Tolerant sp³–sp³ Carbon–Carbon Bond Formations

Asymmetric Baylis-Hillman Reaction: Use of Novel Chiral Aldehydes as Electrophiles, Chiral Base Catalysts and Auxilliaries&#

Contact Info

Product

Resources

About

Stereochemistry of the reactions of substituted allylboronates with chiral aldehydes. Factors influencing aldehyde diastereofacial selectivity

Cited by 171 publications

References 0 publications

Syntheses and Biological Evaluation of (+)-Lactacystin and Analogs

Syntheses and Biological Evaluation of (+)-Lactacystin and Analogs

Palladium(0) versus Nickel(0) Catalysis in Selective Functional‐Group‐Tolerant sp3–sp3 Carbon–Carbon Bond Formations

Asymmetric Baylis-Hillman Reaction: Use of Novel Chiral Aldehydes as Electrophiles, Chiral Base Catalysts and Auxilliaries&#

Contact Info

Product

Resources

About

Palladium(0) versus Nickel(0) Catalysis in Selective Functional‐Group‐Tolerant sp³–sp³ Carbon–Carbon Bond Formations