Radicals of type 1 undergo 5-exo diagonal cyclization, and the resulting vinyl radical abstracts hydrogen from silicon to afford a silicon-centered radical. This radical closes in a 5-endo trigonal manner to generate radicals of type 4, which are reduced (4 --> 5) by stannane, except when the starting acetylene carries a terminal trimethylstannyl group. In this case, radicals 4 expel trimethylstannyl radical to afford vinyl silanes 6. The stereochemical outcome of the radical cascade 1 --> 5 is controlled by the stereochemistry of the oxygen-bearing carbon in 1 (see starred atom). The sequence can be initiated by carbon-, alpha-substituted carbon-, oxyacyl-, and carbamoyl radicals and generates a silicon-containing ring fused onto a carbocycle or heterocycle. Numerous examples are described, as well as a number of transformations of the final cyclization products, especially their response to n-Bu(4)NF and to BF(3).OEt(2), reagents that cleave the newly formed carbon-silicon bond.
Recordings were made from neurons in primary somatosensory (SmI) forepaw cortex of rats to study the time course of changes in responses beginning immediately following denervation (ligation) of a single digit. Before denervation, neuronal receptive fields (RFs) defined by tactile stimulation varied in size from small regions of one digit to larger areas covering several digits and palmar pads. With electrical stimulation, most neurons responded best to one (on-focus) digit and less to other (off-focus) digits; on-focus stimulation yielded more spikes per stimulus and shorter spike latencies (Lmin) than did off-focus stimulation. After ligation of the on-focus digit, most neurons showed increased responsiveness to stimulating one or several off-focus digits and palmar regions of the forepaw: (1) tactile stimulation showed that the RFs of all but one neuron expanded to include previously "ineffective" skin regions, such as digits or palmar pads adjoining the original RF; (2) electrical stimulation usually evoked stronger responses from neighboring off-focus digits and sometimes elicited novel responses from previously ineffective digits--seven of ten neurons showed increases in spikes per stimulus, which tended to approach stable values within 60-90 min after denervation; three of ten neurons showed decreases in Lmin with time, but most revealed no significant changes. These results suggest that dynamic response properties, as well as RFs, of SmI cortical neurons can be modified rapidly by blocking afferent input from dominant on-focus skin regions. RFs expand and novel responses appear, with concomitant increases in response magnitude and, in some cases, decreases in response latency over time. These findings seem to reflect a rapid increase in synaptic efficacy of weak or previously ineffective inputs from cutaneous afferent nerve fibers.
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