TY - JOUR AU - Siddiqui, Saher H.; Navuluri, Chandrasekhar; Charette, André B. TI - Enantioselective Synthesis of cis- and trans-Borocyclopropylmethanol: Simple Building Blocks To Access Heterocycle-Substituted Cyclopropylmethanols SN - 0039-7881 SN - 1437-210X PY - 2019 JO - Synthesis JF - Synthesis LA - EN VL - 51 IS - 20 SP - 3834 EP - 3846 ET - 2019/08/01 DA - 2019/09/30 KW - borocyclopropanes KW - heterocycles KW - Simmons–Smith reaction KW - zinco-cyclopropanation KW - cross-coupling AB - An enantioselective and non-oxidative methodology was developed to obtain enantioenriched cyclopropyl boronates using a diethanolamine-promoted selective decomplexation of dioxaborolane. The non-oxidative decomplexation of the dioxaborolane ligand from the cyclopropylmethoxide species formed in the dioxaborolane-mediated Simmons–Smith cyclopropanation reaction provided the enantio­enriched CIDA-based (CIDA = N-cyclohexyliminodiacetic acid) boro­cyclopropane in 92% yield and 95.6:4.4 er. A robustness screen has shown diethanolamine to be compatible with esters, carbamates and N-heterocycles, providing a tool to access enantioenriched cyclopropanes carrying not only base-sensitive but oxidizable functional groups as well. Diethanolamine was found to be compatible with the modified zinco-cyclopropanation reaction of allyl alcohol to remove residual dioxaborolane from the corresponding cis-N-heterocycle cyclopropylmethanol, thereby leading to improved yields. PB - © Georg Thieme Verlag DO - 10.1055/s-0037-1611896 UR - http://www.thieme-connect.com/products/ejournals/abstract/10.1055/s-0037-1611896 ER -