Solution structures of the mixed aggregates derived from lithium acetylides and a camphor-derived amino alkoxide.
نویسندگان
چکیده
Low-temperature (6)Li, (13)C, and (15)N NMR spectroscopies reveal that mixtures of lithium cyclopropylacetylide or lithium phenylacetylide (RCCLi) and a vicinal amino alkoxide derived from camphor (R*OLi) in THF/pentane afford an asymmetric (RCCLi)(3)(R*OLi) mixed tetramer and a C(2)-symmetric (RCCLi)(2)(R*OLi)(2) mixed tetramer depending on the stoichiometries. The corresponding (RCCLi)(R*OLi)(3) mixed tetramer is not observed. R*OLi-mediated additions of PhCCLi to benzaldehyde proceed with up to an 8:1 enantiomeric ratio that depend on both the choice of R*OLi and the PhCCLi/R*OLi stoichiometries. The results are considered in light of a previously proposed mechanism for the 1,2-addition to a trifluoromethyl ketone.
منابع مشابه
NMR spectroscopic investigations of mixed aggregates underlying highly enantioselective 1,2-additions of lithium cyclopropylacetylide to quinazolinones.
The solution structures of mixed aggregates derived from lithium alkoxides and lithium acetylides were investigated as part of a program to develop practical syntheses of quinazolinone-based nonnucleoside reverse transcriptase inhibitors. Low-temperature (6)Li, (13)C, and (15)N NMR spectroscopies reveal that mixtures of lithium cyclopropylacetylide (RCCLi), a (+)-carene-derived amino alkoxide (...
متن کاملMixed Aggregates of the Dilithiated Koga Tetraamine: NMR Spectroscopic and Computational Studies.
A combination of (1) H, (6) Li, (13) C, and (15) N NMR spectroscopies and density functional theory computations explores the formation of mixed aggregates by a dilithium salt of a C2 -symmetric chiral tetraamine (Koga's base). Lithium halides, acetylides, alkoxides, and monoalkylamides form isostructural trilithiated mixed aggregates with few exceptions. (6) Li-(13) C and (6) Li-(15) N couplin...
متن کاملMixed Aggregates of 1-Methoxyallenyllithium with Lithium Chloride
A combined computational and (13)C NMR study was used to investigate the formation of mixed aggregates of 1-methoxyallenyllithium and lithium chloride in tetrahydrofuran (THF) solution. The observed and calculated chemical shifts, as well as the calculated free energies of mixed aggregate formation (MP2/6-31+G(d)), are consistent with the formation of a mixed dimer as the major species in solut...
متن کاملRing Cleavage of Some Bicylic Compounds Derived from 1,2,4-Triazine
Ring cleavage occurred when 1,2,4-triazino-1,2,4-triazines (3), (4) and (5) were treated with concentrated hydrochloric acid to yield N-substituted triazines (7) and (8). These confirm the given configuration assigned to the isomeric triazinotriazines. 6-Methyl-2-phenyl-7H-oxazolo [3,2-b][1,2,4]-triazin-7-one (9) underwent ring cleavage on treatment with sodium alkoxide to afford 3-alkoxy-1...
متن کاملSYNTHESIS OF AMINO DERIVATIVE OF INDENE AND FLUORENE FROM IMIMIUM SALT GENERATED IN ETHEREAL LITHIUM PERCHLORATE SOLUTION
A series of amino derivative of 1-indene and 9-fluorene have been synthesized from their corresponding iminium salt, generated in situ in the concentrated ethereal lithium perchlorate solution, and 1-indenyl or 9-fluorenyl anions. The yields of the reactions depend on the kind of anion. Addition of 1-indeny anion to the iminium salt gives the amino derivative of 1-indene, while addition of fluo...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- The Journal of organic chemistry
دوره 66 19 شماره
صفحات -
تاریخ انتشار 2001