The circumambulation of a phosphirane: Taking 9-phenyl-9-phosphabicyclo[6.1.0]nona-2,4,6-triene for a "walk"
The circumambulation of a phosphirane: Taking 9-phenyl-9-phosphabicyclo[6.1.0]nona-2,4,6-triene for a "walk"
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DOI：
10.1002/anie.200351855
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发表时间：
2004-01-01
影响因子：
16.6
通讯作者：
Lammertsma, K
中科院分区：
文献类型：
--
作者：
Bulo, RE;Jansen, H;Lammertsma, K
“Walk” rearrangements are also known for 1, 2, and 5, with sulfur, nitrogen, or oxygen as the migrating atom,[1] but not with phosphorus, though a degenerate rearrangement along part of a ring has been reported for a triphospha analogue of 1, with a weak phosphorus–phosphorus bond.[4] Whereas thio,[5] oxa,[6] amino,[7] and phospha analogues [8] of 3 are known, the potential for “walk” activity has not been recognized for any. Herein we present the first such bishapto eight-electron phosphirane circumambulation for 3P (E= PPh).The reaction of the cyclooctatriene dianion with dichlorophenylphosphane affords exclusively exo-3P, the crystal structure of which is shown in Figure2. The 1H NMR spectrum of 3P does not display noticeable line broadening at 300 K, but on selective inversion (by a DPFGE (doublepulsed field-gradient spin echo) sequence)[9] of one of the ring
