The mechanism of photochemical 1,3-silyl migration of allylsilane

Takahashi M

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The mechanism of photochemical 1,3-silyl migration of allylsilane

机译：烯丙基硅烷的光化学1,3-甲硅烷基迁移机理

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The photochemical reaction mechanisms of model compounds for 4-tert-butyl-1-(4-phenylphenyl)-1-(1,1-dimethylallyl)silacyclohexane are investigated using a complete active space comprised of six electrons in six orbitals with the standard 6-31G(d) basis set. It is concluded that the stereochemistry in the photochemical 1,3-silyl migrations of allylsilanes has a retention preference, in accord with the Woodward-Hoffmann rules. The calculated conical intersection (CI) structure suggests a dissociation path to radicals in addition to a 1,3-shift path. The bulkiness and rigidness of a silacyclohexane moiety does not affect the stereochemistry, but a slightly elongated Si-C bond length in the CI structure would promote the dissociation path.

机译：使用由六个轨道上的六个电子组成的，具有标准6的完整活性空间，研究了4-叔丁基-1-（4-苯基苯基）-1-（1,1-二甲基烯丙基）硅环己烷中模型化合物的光化学反应机理。 -31G（d）基集。结论是，根据Woodward-Hoffmann规则，烯丙基硅烷的光化学1,3-甲硅烷基迁移中的立体化学具有保留优先权。计算出的圆锥形相交（CI）结构表明，除1,3位移路径外，还具有离解基团。硅环己烷部分的体积和刚度不影响立体化学，但是CI结构中Si-C键长度稍长会促进解离路径。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |2005年第51期|共5页
作者
Takahashi M;
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正文语种 eng
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CARBON UNSATURATED-COMPOUNDS; ORGANO-SILICON COMPOUNDS; ORGANOSILICON COMPOUNDS; THERMAL REARRANGEMENT; FORBIDDEN REACTIONS; ORBITAL-SYMMETRY; AB-INITIO; PHOTOLYSIS; STEREOCHEMISTRY; CHEMISTRY;

机译：碳非饱和化合物;有机硅化合物;有机硅化合物;热重排;禁忌反应;轨道对称性;AB INITIIO;光解;立体化学;化学性质;

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1. The mechanism of photochemical 1,3-silyl migration of allylsilane [J] . Takahashi M The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory . 2005,第51期

机译：烯丙基硅烷的光化学1,3-甲硅烷基迁移机理
2. Novel Aspects of the [1,3] Sigmatropic Silyl Shift in Allylsilane [J] . Tokio Yamabe, Koichi Nakamura, Yoshihito Shiota Journal of the American Chemical Society . 1997,第4期

机译：烯丙基硅烷中[1,3]σ甲硅烷基转移的新颖方面
3. 1,2- versus 1,3-Silyl migration in the reaction of acylsilanes with silyl-substituted carbanions [J] . Thomas Puschke, Jens Lange, Ernst Schaumann Tetrahedron letters: The International Journal for the Rapid Publication of Preliminary Communications in Organic Chemistry . 2008,第16期

机译：酰基硅烷与甲硅烷基取代的碳负离子反应中的1,2-与1,3-甲硅烷基迁移
4. Boron Trifluoride-catalyzed Reaction of Alkyl Fluoride with Silyl Enolate,Allylsilane,and Hydrosilane [C] . Koji Hirano, Kazuya Fujita, Hideki Yorimitsu, Symposium on Organometallic Chemistry . 2004

机译：硼三氟化铝催化烷基氟化物与甲硅烷基烯醇，烯丙基硅烷和氢硅烷反应
5. Products and mechanisms of the reactions of chlorine atoms with 1,3-butadiene and 2-methyl-1,3-butadiene (Isoprene) in air at room temperature. [D] . Wang, Wezhong. 2000

机译：室温下空气中氯原子与1,3-丁二烯和2-甲基-1,3-丁二烯（异戊二烯）反应的产物和机理。
6. RationalDesign of a Second Generation Catalyst forPreparation of Allylsilanes Using the Silyl-Heck Reaction [O] . JesseR. McAtee, Glenn P. A. Yap, Donald A. Watson, -1

机译：合理的第二代催化剂的设计使用甲硅烷基-Heck反应制备烯丙基硅烷
7. Rearrangement Approaches to Cyclic Skeletons. IV. The Total Synthesis of (±)-Pinguisone and (±)-Deoxopinguisone Based on Photochemical 1,3 Acyl Migration of a Bicyclo3.2.2non-6-en-2-one [O] . Tadao Uyehara, Yasuhiro Kabasawa, Tadahiro Kato 1986

机译：重新排列循环骨骼的方法。 IV。（±） - 法比松的总合成和（±） - 基于光化学1,3酰基迁移的（±1,3乙酰偏移3.2.2非6-en-2-one
8. Photochemical Reactions of (n(5)-Pentamethylcyclpentadienyl)-Dicarbonyliron-Alkyl and -Silyl Complexes: Reversible Ethylene Insertion into an Iron-Silicon Bond and Implications for the Mechanism of Transition Metal-Catalyzed Hydro [R] . Randolph, C. L., Wrighton, M. S. 1985

机译：（n（5） - 十六烷基环戊二烯基） - 二羰基铁 - 烷基和 - 甲硅烷基配合物的光化学反应：可逆乙烯插入铁 - 硅键并对过渡金属催化的水解机理的影响

The mechanism of photochemical 1,3-silyl migration of allylsilane

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