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1,2-Thiaphosphetanes: The Quest for Wittig-Type Ring Cleavage, Rearrangement, and Sulfur Atom Transfer.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-02-12 , DOI: 10.1021/acs.inorgchem.9b03471 Arturo Espinosa Ferao 1 , Rainer Streubel 2
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-02-12 , DOI: 10.1021/acs.inorgchem.9b03471 Arturo Espinosa Ferao 1 , Rainer Streubel 2
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The potential energy surface for opening and ring-enlargement reactions of 1,2-thiaphosphetane with different oxidation states and coordination at phosphorus has been computationally explored. The most favored [2 + 2] cycloreversions are the so-called normal Wittig-type reactions furnishing an alkene and a P═S-containing component. Somewhat unfavored are reactions involving the P-S bond cleavage and a C-to-P hydrogen shift as well as a ring enlargement to a 1,3,2-dithiaphospholane in the case of high coordinate derivatives. Apart from a two-step P-to-S oxygen transfer in 1,2σ4λ5-thiaphosphetane P-oxide, an interesting reaction is the P-S bond cleavage leading to a thiabetaine which, alternatively, can be formed by the C-attack of a phosphinidene oxide on a thiirane. A similar route, energetically more favored, was found for 1,2σ5λ5-thiaphosphetane starting from thiirane and the corresponding phosphane. For a wide set of P(III) reagents including HPR2 (R = Me, Ph), PR3 (R = Me, Ph, NMe2, OMe, F, Cl), and HP═O, the competitive direct S-attack was found to be the preferred pathway for the desulfurization of thiiranes, and the relative tendency for these P(III) reagents to act as an S-atom acceptor, the thermodynamic S-transfer potential (TSP) scale, was defined using the S8/S7 couple as a point of reference.
中文翻译：
1,2-硫代磷杂环丁烷：对维蒂希型环裂解，重排和硫原子转移的追求。
通过计算探索了具有不同氧化态和磷配位的1,2-硫代磷杂环丁烷的开环和扩环反应的势能面。最优选的[2 + 2]环还原反应是提供烯烃和含P═S组分的所谓常规Wittig型反应。在高配位衍生物的情况下，涉及PS键断裂和C到P的氢转移以及环扩大为1,3,2-二硫代膦烷的反应有些不利。除了在1,2σ4λ5-硫代磷烷P-氧化物中进行两步P-S氧转移外，有趣的反应是PS键断裂导致硫代甜菜碱，该硫代甜菜碱可以通过次膦的C-攻击形成硫杂环丁烷上的氧化物。发现了一条在能量上更受青睐的类似路线：从硫杂环丁烷和相应的膦开始的2σ5λ5-硫杂磷环。对于包括HPR2（R = Me，Ph），PR3（R = Me，Ph，NMe2，OMe，F，Cl）和HP = O在内的多种P（III）试剂，发现了竞争性直接S攻击是硫烷脱硫的首选途径，并且使用S8 / S7对定义了这些P（III）试剂充当S原子受体的相对趋势，即热力学S转移势（TSP）标度。作为参考。
更新日期：2020-02-13
中文翻译：
1,2-硫代磷杂环丁烷：对维蒂希型环裂解，重排和硫原子转移的追求。
通过计算探索了具有不同氧化态和磷配位的1,2-硫代磷杂环丁烷的开环和扩环反应的势能面。最优选的[2 + 2]环还原反应是提供烯烃和含P═S组分的所谓常规Wittig型反应。在高配位衍生物的情况下，涉及PS键断裂和C到P的氢转移以及环扩大为1,3,2-二硫代膦烷的反应有些不利。除了在1,2σ4λ5-硫代磷烷P-氧化物中进行两步P-S氧转移外，有趣的反应是PS键断裂导致硫代甜菜碱，该硫代甜菜碱可以通过次膦的C-攻击形成硫杂环丁烷上的氧化物。发现了一条在能量上更受青睐的类似路线：从硫杂环丁烷和相应的膦开始的2σ5λ5-硫杂磷环。对于包括HPR2（R = Me，Ph），PR3（R = Me，Ph，NMe2，OMe，F，Cl）和HP = O在内的多种P（III）试剂，发现了竞争性直接S攻击是硫烷脱硫的首选途径，并且使用S8 / S7对定义了这些P（III）试剂充当S原子受体的相对趋势，即热力学S转移势（TSP）标度。作为参考。
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