Copper-Catalyzed 1,2-Addition of Nucleophilic Silicon to Aldehydes: Mechanistic Insight and Catalytic Systems

• Published in: Chemistry : a European journal Vol. 17; no. 48; pp. 13538 - 13543
• Main Authors: Kleeberg, Christian, Feldmann, Evgenia, Hartmann, Eduard, Vyas, Devendra J., Oestreich, Martin
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 25.11.2011; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Subjects: Alcohol; Aldehydes; Chemistry; Chemistry, Multidisciplinary; Copper; nucleophilic addition; Physical Sciences; Science & Technology; silicon; transmetalation; X-ray diffraction; SUBSTITUTION; HYDROGENATION; B BOND ACTIVATION; CONJUGATE SILYL TRANSFER; COMPLEXES; X-ray diffraction; aldehydes; silicon; REDUCTION; ALPHA,BETA-UNSATURATED ACCEPTORS; copper; SILYLBORANES; 1,4-ADDITION; nucleophilic addition; transmetalation; ACYL SILANES
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/chem.201102367

Activation of the SiB inter‐element bond with copper(I) alkoxides produces copper‐based silicon nucleophiles that react readily with aldehydes to yield α‐silyl alcohols (that is, α‐hydroxysilanes) after hydrolysis. Two independent protocols were developed, one employing a well‐defined NHCCuOtBu complex and one using the simple CuCN–NaOMe combination without added ligand. The mechanism of the aldehyde addition was investigated in detail by stoichiometric and catalytic experiments as well as NMR spectroscopic measurements. The primary reaction product of the addition of the SiB reagent and the aldehyde (a boric acid ester of the α‐silyl alcohol) and also the “dead‐end” intermediate, formed in the competing [1,2]‐Brook rearrangement, were characterized crystallographically. Based on these data, a reasonable catalytic cycle is proposed. The NHCCuOtBu catalytic setup performs nicely at elevated temperature. A more reactive catalytic system is generated from CuCN–NaOMe, showing fast turnover at a significantly lower temperature. Both aromatic and aliphatic aldehydes are transformed into the corresponding α‐silyl alcohols in good to very good yields under these mild reaction conditions. Excellent exchange rate! The 1,2‐addition of silicon nucleophiles to aldehydes is investigated in detail by stoichiometric and catalytic experiments and NMR spectroscopy. The transmetalation step is faster than the competing [1,2]‐Brook rearrangement (see scheme). Two independent protocols were developed; one employs a well‐defined NHCCuOtBu complex and one uses a simple CuCN–NaOMe combination without added ligand.