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31.
Earlier we noted that the hydroboration of the trimethylsilyl enol ether of an acyclic ketone results in an elimination of a trimethylsiloxyborane moiety with the subsequent formation of an olefin.1,2 The olefin formed then undergoes hydroboration giving a monoalcohol upon oxidation. (eq 1) We wish to report here on the utility of this sequence, illustrated in eq 1, in the reductive 1,2 transposition of acyclic ketones.3 相似文献
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It has been shown that tert-butyldimethylsilylated (Z) 2-carboethoxymethylene cycloalkanols are readily desilylated with concomitant cyclization to give the corresponding butenolides. The (E) isomers are desilylated, but not cyclized under these conditions. 相似文献
34.
The utility of organoboranes in the synthesis of a wide variety of functional groups is now well established.1 There have been, however, only a limited number of reports where an organoborane containing a β-functionalized carbon was utilized in organic synthesis. Part of the reason for this is the difficulty in preparing β-functional organoboranes and their tendency to undergo elimination under a variety of reaction conditions.2 Those β-functionalized organoboranes utilized synthetically, which we could find in the literature are the β-ethoxy3, 1, and β-carboethoxyvinyl-boranes4, 2, of Zweifel and coworkers and the trans-β-tert-butyldimethylsilyloxy organoborane, 3, of Corey and Ravindranathan,5 who proposed this system as a potential precursor to prostanoids. 相似文献
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Ronald G. Larson 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2012,124(11):2596-2598
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[reaction: see text] A general set of conditions that achieves the union of aryl halides and divinyl or enyne carbinols to afford tri- or tetrasubstituted olefins in good yields (up to 83%) is described. The mechanism by which this proceeds is believed to involve the intermediacy of a cyclopropanol, followed by a novel skeletal reorganization. The ability to suppress beta-hydride elimination of organopalladium intermediates appears to be critical to the success of these processes. 相似文献
40.
Sivasankar M Bauer JJ Babu T Larson CR 《The Journal of the Acoustical Society of America》2005,117(2):850-857
The present study was undertaken to examine if a subject's voice F0 responded not only to perturbations in pitch of voice feedback but also to changes in pitch of a side tone presented congruent with voice feedback. Small magnitude brief duration perturbations in pitch of voice or tone auditory feedback were randomly introduced during sustained vowel phonations. Results demonstrated a higher rate and larger magnitude of voice F0 responses to changes in pitch of the voice compared with a triangular-shaped tone (experiment 1) or a pure tone (experiment 2). However, response latencies did not differ across voice or tone conditions. Data suggest that subjects responded to the change in F0 rather than harmonic frequencies of auditory feedback because voice F0 response prevalence, magnitude, or latency did not statistically differ across triangular-shaped tone or pure-tone feedback. Results indicate the audio-vocal system is sensitive to the change in pitch of a variety of sounds, which may represent a flexible system capable of adapting to changes in the subject's voice. However, lower prevalence and smaller responses to tone pitch-shifted signals suggest that the audio-vocal system may resist changes to the pitch of other environmental sounds when voice feedback is present. 相似文献