Catalytic enantioselective dehydrogenative Si–O coupling of oxime ether-functionalized alcohols

• Published in: Tetrahedron Vol. 68; no. 17; pp. 3468 - 3479
• Main Authors: Weickgenannt, Andreas, Mohr, Jens, Oestreich, Martin
• Format: Journal Article
• Language: English
• Published: OXFORD Elsevier Ltd 29.04.2012; Elsevier
• Subjects: Alcohols; Byproducts; Catalysts; Chemistry; Chemistry, Organic; Copper; Dehydrogenation; Enantioselective silylation; Joining; Kinetic resolution; Oxime ethers; Oximes; Physical Sciences; Reaction kinetics; Science & Technology; Silanes; Silicon; MNQGPFZDJUROLT-SANMLTNESA-N; CSCPPACGZOOCGX-UHFFFAOYSA-N; QOLXJHDVGVFDGR-UHFFFAOYSA-N; PWMWNFMRSKOCEY-MRVPVSSYSA-N; OEKUTWAWBRHWCM-UHFFFAOYSA-N; FDPIMTJIUBPUKL-UHFFFAOYSA-N; NSWLIILRPYRYBB-UHFFFAOYSA-N; MYNLVFCDVFSJLK-UHFFFAOYSA-N; JMZPAYBTIPFYTP-YTTGMZPUSA-N; RLCLQJYIHKSICW-UHFFFAOYSA-N; LGNBNHVCNYLVHA-UHFFFAOYSA-N; HODHLSXWJXXKJW-QGZVFWFLSA-N; BRGXOIHNMVMFIC-ZOYWYXQUSA-N; Copper; ALTZLMZVUDPXFN-NRFANRHFSA-N; GPDFIKFKQYAZRZ-UHFFFAOYSA-N; DJZNNYQWQBEXBR-SANMLTNESA-N; WACXPYNJZBUTDY-UHFFFAOYSA-N; RKFKZOYLXUQXJK-UHFFFAOYSA-N; CPGUTPWHSDASLW-PMERELPUSA-N; NDILJRBINRADDU-DEOSSOPVSA-N; JRWFWDGPASIQTC-UHFFFAOYSA-N; XFBJQPKDQUCCHE-DEOSSOPVSA-N; AAURXTKLVUIKIM-FYCDPJMQSA-N; JLVRMWOUPWZGOG-UHFFFAOYSA-N; AQRLNPVMDITEJU-UHFFFAOYSA-N; FALTZKHAEBNAEH-RVDMUPIBSA-N; BGGPNRFXYWREFM-IBGZPJMESA-N; PJGSXYOJTGTZAV-UHFFFAOYSA-N; GOLHJMJCRFQWNY-UHFFFAOYSA-N; XJVRGIVNDSHUQW-UHFFFAOYSA-N; Kinetic resolution; WUTQCOIYEBMXCN-UHFFFAOYSA-N; VZPFKVPQLYHGEC-UHFFFAOYSA-N; QJEMLWPMIJJTSN-SANMLTNESA-N; FULSRCPEOUATID-UHFFFAOYSA-N; FXYOFVQXBYZHDJ-UHFFFAOYSA-N; VTTGYMYSMCCTKS-UHFFFAOYSA-N; FHEYGISAROMHEF-RBISFHTESA-N; JITBDKGHCDQACA-UHFFFAOYSA-N; CZNBFYCMCCHCPW-UHFFFAOYSA-N; OEDDQYCIMJYAHI-UHFFFAOYSA-N; JROQHJYILKSVBP-DEOSSOPVSA-N; RRUDCFGSUDOHDG-UHFFFAOYSA-N; GSDCIWXHRVLCCF-UHFFFAOYSA-N; ZISUALSZTAEPJH-UHFFFAOYSA-N; DAQDRNPWUJKIIJ-NDEPHWFRSA-N; NMPYOGVZLNIITA-GHRIWEEISA-N; USIUVYZYUHIAEV-UHFFFAOYSA-N; HXVNBWAKAOHACI-UHFFFAOYSA-N; Silicon; OUIDZUVHQGOINW-DEOSSOPVSA-N; DXHIFWXHVRVCPJ-UHFFFAOYSA-N; OYDRVSGRJCOTFQ-UHFFFAOYSA-N; PFPSMIHWTKVWJR-UHFFFAOYSA-N; SQFDDIDKOBLDKP-UHFFFAOYSA-N; YPYKZPHMCIBVPH-QABMSTFYSA-N; ZBGUJLMFXIUKNZ-KRWDZBQOSA-N; XTIBSYVUDLOHEC-VWLOTQADSA-N; Oxime ethers; ZNULKKNNZDXBGY-NRFANRHFSA-N; SCQQNLYSFBRTAB-UHFFFAOYSA-N; RCNOCKMWJSQPAB-VWLOTQADSA-N; XLIKYWYJMHTSTM-NDEPHWFRSA-N; IEGUSFCTHSZXKK-LLVKDONJSA-N; LMARXYWDYPGKSM-QFIPXVFZSA-N; BSHFAFZNMZKRSY-UHFFFAOYSA-N; HPJPYUZLPFWEBQ-UHFFFAOYSA-N; ZLBWPYIKHLGYQC-UHFFFAOYSA-N; KWOLFJPFCHCOCG-UHFFFAOYSA-N; Enantioselective silylation; RPNLXFSEQGCGRQ-UHFFFAOYSA-N; XEGZTSZGIHXOHN-DEOSSOPVSA-N; CHGMLLMTYYHYTM-UHFFFAOYSA-N; PROTECTION; MECHANISM; SCOPE; REACTIVITY; NONENZYMATIC KINETIC RESOLUTION; STEREOSELECTIVE SILYLATION; SILICON-STEREOGENIC SILANES; SECONDARY ALCOHOLS; EPOXIDES; LIGANDS
• ISSN: 0040-4020; 1464-5416
• DOI: 10.1016/j.tet.2011.06.102

Asymmetric silylation of alcohols is an unusual but effective approach to their kinetic resolution, and the Cu–H-catalyzed dehydrogenative Si–O coupling is particularly noteworthy as dihydrogen is formed as the sole by-product. Our laboratory had previously reported on diastereoselective (with silicon-stereogenic silanes) and enantioselective (with achiral silanes) Si–O couplings of azine donor-functionalized alcohols. The limitation, that is, the requirement of a nitrogen donor atom, prompted us to seek equally useful donor groups. Oxime ethers were identified as a suitable alternative, and we describe herein the preparation of a series of oxime ether-functionalized alcohols. To assess different substitution patterns in their kinetic resolution, these were tested in the reagent-controlled Si–O coupling using a silicon-stereogenic silane. The optimal substituents at the oxime carbon atom (dr=85:15 in the diastereoselective coupling) were then chosen for the related catalyst-controlled Si–O coupling but selectivity factors were only moderate. [Display omitted]