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31.
Conformationally biased cyclohexylideneethanols were prepared and converted to trichloroacetimidates, which then were subjected to the thermal Overman rearrangement. The rearrangement of axially unshielded imidates was unselective, providing isomeric amides in equal ratio. The axial face shielding in the 3,3,5-trimethylcyclohexylidene system resulted in highly selective nitrogen attack from the equatorial side. 相似文献
32.
Dr. Tomas Javorskis Dr. Ieva Karpavičienė Arminas Jurys Gustautas Snarskis Dr. Rita Bukšnaitienė Prof. Edvinas Orentas 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(45):20295-20303
Catalyst-free addition of ketone enolate to non-activated multiple C−C bonds involves non-complementary reaction partners and typically requires super-basic conditions. On the other hand, highly aggregated or solvated enolates are not reactive enough to undergo direct addition to alkenes or alkynes. Herein, we report a new anionic cascade reaction for one-step assembly of intriguing molecular scaffolds possessing contiguous six-, five-, and four-membered rings, representing a formal [2+2] enol–allene cycloaddition. Reaction proceeds under very mild conditions and with excellent diastereoselectivity. Deeper mechanistic and computational studies revealed unusually slow proton transfer phenomenon in cyclic ketone intermediate and explained peculiar stereochemical outcome. 相似文献
33.
Mayur Shah Kannappan Thangaraj Mou-Ling Soong Lionel T. Wolford Joseph H. Boyer Ieva R. Politzer Theodore G. Pavlopoulos 《Heteroatom Chemistry》1990,1(5):389-399
Condensations between 3-X-2,4-dimethylpyrroles (X = H, CH3, C2H5, and CO2C2H5) and acyl chlorides gave derivatives of 3,5,3′,5′-tetramethylpyrromethene (isolated as their hydrochloride salts): 6-methyl, 6-ethyl, 4,4′,6-trimethyl, 4,4′-diethyl-6-methyl, and 4,4′-dicarboethoxy-6-ethyl derivatives for conversion on treatment with boron trifluoride to 1,3,5,7-tetramethylpyrromethene–BF2 complex (TMP–BF2) and its 8-methyl (PMP–BF2), 8-ethyl, 2,6,8-trimethyl (HMP–BF2),2,6,-diethyl-8-methyl (PMDEP–BF2), and 2,6-dicarboethoxy-8-ethyl derivatives. Chlorosulfonation converted, 1,3,5,7,8-pentamethylpyrromethene–BF2 complex to its 2,6-disulfonic acid isolated as the lithium, sodium (PMPDS–BF2), potassium, rubidium, cesium, ammonium, and tetramethylammonium disulfonate salts and the methyl disulfonate ester. Sodium 1,3,5,7-tetramethyl-8-ethylpyrromethene-2,6-disulfonate–BF2 complex was obtained from the 8-ethyl derivative of TMP–BF2. Nitration and bromination converted PMP–BF2 to its 2,6-dinitro-(PMDNP–BF2) and 2,6-dibromo- derivatives. The time required for loss of fluorescence by irradiation from a sunlamp showed the following order for P–BF2 compounds (10−3 to 10−4 M) in ethanol: PMPDS–BF2, 7 weeks; PMP–BF2, 5 days; PMDNP–BF2, 72 h; HMP–BF2, 70 h; and PMDEP–BF2, 65 h. Under similar irradiation PMPDS–BF2 in water lost fluorescence after 55 h. The dibromo derivative was inactive, but each of the other pyrromethene–BF2 complexes under flashlamp excitation showed broadband laser activity in the region λ 530–580 nm. In methanol PMPDS–BF2 was six times more resistant to degradation by flashlamp pulses than was observed for Rhodamine-6G (R-6G). An improvement (up to 66%) in the laser power efficiency of PMPDS–BF2 (10−4 M in methanol) in the presence of caffeine (a filter for light <300 nm) was dependent on flashlamp pulse width (2.0 to 7.0 μsec). 相似文献