Tertiary α‐Silyl Alcohols by Diastereoselective Coupling of 1,3‐Dienes and Acylsilanes Initiated by Enantioselective Copper‐Catalyzed Borylation

• Published in: Angewandte Chemie International Edition Vol. 58; no. 24; pp. 8211 - 8215
• Main Authors: Feng, Jian‐Jun, Oestreich, Martin
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 11.06.2019; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alcohol; Alcohols; Aromatic compounds; asymmetric catalysis; boron; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Copper; Coupling; Dienes; Enantiomers; multicomponent reactions; Physical Sciences; Science & Technology; silicon; Stereoselectivity; multicomponent reactions; BOND FORMATION; asymmetric catalysis; ARYLBORATION; ALLENES; BROOK REARRANGEMENT; silicon; BIS(PINACOLATO)DIBORON; ALDOL REACTION; copper; GENERATION; 2 STEREOCENTERS; ADDITIONS; boron; IN-SITU
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201903174

An efficient synthesis of functionalized tertiary α‐silyl alcohols by an enantio‐ and diastereoselective copper‐catalyzed three‐component coupling of 1,3‐dienes, bis(pinacolato)diboron, and acylsilanes is reported. The reaction proceeds well with different 1,3‐dienes and a broad range of aryl‐ as well as alkenyl‐ but also alkyl‐substituted acylsilanes. The target compounds are formed with high regio‐, diastereo‐, and enantioselectivity (up to 99 % ee and d.r. >20:1) and are highly versatile synthetic building blocks. All at once: A copper‐catalyzed three‐component coupling of 1,3‐dienes, bis(pinacolato)diboron, and acylsilanes affords densely functionalized tertiary α‐silyl alcohols regioselectively in high yields as well as with excellent enantioselectivity (up to 99 % ee) and diastereoselectivity (d.r. >20:1). Subsequent transformations illustrate the versatility of these chiral building blocks.