Enantioselective Synthesis of Allylboronates and Allylic Alcohols by Copper‐Catalyzed 1,6‐Boration

Stereoselective synthesis of 3-hydroxy-3-methylglutaryl–coenzyme A reductase inhibitors

“…2MeOH/Li and a Josiphos ligand 115 in their efforts towards the synthesis of atorvastatin (Scheme 53). 116 The α,β,γ,δ-unsaturated ester 268 (a mixture with E/Z = 16:1) was prepared in two steps from 194, and subjected to catalytic enantioselective 1,6-boration using a 0.02% Cu I -Josiphos complex which, upon oxidation of the resulting allboronate with NaBO 3 . 4H 2 O, provided allylic alcohol 269 with 84% ee.…”

Asymmetric Catalytic Borylation of α,β-Unsaturated Acceptors

“…Recently, Lam and co-workers reported that chiral secondary allyboronates can be obtained by selective 1,6-addition (boron addition to the δ-carbon) of α,β,γ,-δ-unsaturated esters and ketones [34]. The regioselectivity was greatly affected by the choice of copper-ligand complexes.…”

Enantioselective γ-borylation of unsaturated amides and stereoretentive Suzuki–Miyaura cross-coupling

“…CAHB by pinBH (0.5% [Rh(nbd) 2 BF 4 /2 ( R )- L1 ]) followed by oxidation affords chiral γ-hydroxy amide ( S )- 7a in 79% overall yield (97 : 3 er). While conjugate addition 11 and C–H activation 10 a methodologies provide efficient alternatives to CAHB for enantioselective β-borylation of carbonyl compounds, direct γ-borylation is unique to CAHB.…”