查看“︁西蒙斯–史密斯反应”︁的源代码

{{NoteTA
|1=zh-tw:碳烯; zh-hans:卡宾;
}}
{{Infobox industrial process
|name = 西蒙斯－史密斯反應
|image = Simmons-Smith carbene addition.jpg
|caption = 正在進行的西蒙斯-史密斯反應
}}
{{Reactionbox
|Name = 西蒙斯－史密斯反應
|Type = 成环反应
|NamedAfter = [[Howard Ensign Simmons, Jr.]] <br /> [[Ronald D. Smith]]
|Section3 = {{Reactionbox Identifiers
|OrganicChemistryNamed = simmons-smith-reaction
|RSC_ontology_id = 0000258
}}
}}
'''Simmons–Smith反应'''（西蒙斯－史密斯反应）是[[烯烃]]或[[炔烃]]与{{link-en|类卡宾|carbenoid}}发生反应生成[[环丙烷]]环系的[[有机反应]]。<ref>{{cite journal en| author = [[Howard Ensign Simmons, Jr.]]; Smith, R.D. | title = 4-Substituted-2,3,5-pyrrolidinetriones | journal = [[J. Am. Chem. Soc.]] | year = 1958 | volume = 80 | pages = 532 | doi = 10.1021/ja01548a031}}.</ref><ref>{{cite journal en| author = Simmons, H.E.; Smith, R.D. | title = A New Synthesis of Cyclopropanes | journal = [[J. Am. Chem. Soc.]] | year = 1959 | volume = 81 | pages = 4256 | doi = 10.1021/ja01525a036}}</ref><ref>{{cite journal en| author = Denis, J.M.; Girard, J.M.; Conia, J.M | journal = [[Synthesis (journal)|Synthesis]] | year = 1972 | pages = 549 | doi = 10.1055/s-1972-21919 | title = Improved Simmons-Smith Reactions | url = https://archive.org/details/sim_synthesis_1972-10_10/page/549 | volume = 1972}}</ref> 此反应以发现者{{link-en|Howard Ensign Simmons, Jr.|Howard Ensign Simmons, Jr.}}和R. D. Smith命名。
:[[File:Simmons-Smith reaction mechanism.png|700px|Simmons-Smith反应机理]]

这个反应用到的类卡宾试剂称为Simmons-Smith试剂，是个[[有机锌化合物]]，通式X(CR<sup>1</sup>R<sup>2</sup>)ZnY，一般为{{link-en|碘化碘甲基锌|iodomethylzinc iodide}}（ICH<sub>2</sub>ZnI）。它一般通过1,1-二卤化物与[[锌铜偶]]（Zn(Cu)）在醚类溶剂中反应制取。最常用的1,1-二卤代烃为[[二卤甲烷]]，如[[二碘甲烷]]。锌铜偶由锌粉在[[硫酸铜]]的酸性溶液中处理活化而得。也可以用[[二乙基锌]]代替锌铜偶。

反应中Simmons-Smith试剂可以提前制取，也可以在反应中原位生成而参加反应。与[[格氏试剂]]的[[Schlenk平衡]]类似，Simmons-Smith试剂也存在如下平衡：
:<math>\rm \ 2 ICH_2ZnI \ \rightleftharpoons \ (ICH_2)_2Zn \ + \ ZnI_2</math>

== 应用 ==
[[环己烯]]与二碘甲烷在锌铜偶的作用下，经过ICH<sub>2</sub>ZnI这一中间体（类卡宾），可以生成[[降蒈烷]]（二环[4.1.0]庚烷）<ref>{{OrgSynth | author = Smith, R. D.; Simmons, H. E. | title = Norcarane | collvol = 5 | collvolpages = 855 | prep = cv5p0855}}</ref><ref>{{OrgSynth | author = Ito, Y.; Fujii, S.; Nakatuska, M.; Kawamoto, F.; Saegusa, T. | collvol = 6 | collvolpages = 327 | year = 1988 | prep = cv6p0327 | title = One-Carbon Ring Expansion Of Cycloalkanones To Conjugated Cycloalkenones: 2-Cyclohepten-1-one}}</ref>

:[[File:Simmons-Smith cyclohexene to bicyclo-4.1.0-heptane.svg|300px|Simmons-Smith反应的例子]]

Simmons–Smith反应是[[立体专一]]的[[顺式]][[加成反應|加成]]。通常受[[位阻效应]]的影响，反应在双键位阻较小的一侧发生。<ref>{{cite journal en| author = Simmons, H. E. ''et al.'' | journal = [[Org. React.]] | year = 1973 | volume = 20 | pages = 1 | format = Review}}</ref><ref>{{cite journal en| author = Girard, C.; Conia, J. M. | journal = [[J. Chem. Res. (S)]] | year = 1978 | pages = 182 | format = Review}}</ref> 但是，当双键上连有一个手性碳，该手性碳上又连有羟基取代基时，由于羟基可以与锌配位，反应往往在羟基的同侧发生，尽管这时的空阻可能较大：<ref>{{cite journal en| title = Stereochemistry and total synthesis of (±)-ivangulin | author = Paul A. Grieco, Tomei Oguri, Chia-Lin J. Wang, and Eric Williams | journal = [[J. Org. Chem]] | year = 1977 | volume = 42 | pages = 4113 | doi = 10.1021/jo00445a027}}</ref>

:[[File:SimmonsSmithhydroxylEffect.svg|300px|一个立体选择性的Simmons-Smith反应]]

Simmons-Smith试剂可以和烯丙基硫醚反应生成[[硫]][[叶立德]]。产物可以发生[[2,3-σ迁移反应]]，得不到环丙烷环系。（试剂过量时，可以进一步反应生成环丙烷环系）<ref>{{cite journal en| author = Cohen, T.; Kosarych, Z. | title = Complete regio- and stereospecificity in the Lewis acid catalyzed Diels-Alder reactions of (Z)-2-methoxy-1-(phenylthio)-1,3-butadienes. Conversion of the CS configuration of an adduct to the CC configuration at the allylic position by a [2,3] sigmatropic rearrangement | journal = [[J. Org. Chem]] | year = 1982 | volume = 47 | pages = 4005 | doi = 10.1021/jo00141a047}}</ref>

:[[File:Simmons smith quaternary carbon rearrangement.svg|500px|例子：用Simmons-Smith反应生成硫叶立德]]

== 不对称Simmons-Smith反应 ==
尽管基于[[重氮]]化合物的环丙烷环系的不对称合成法早在1966年就已经出现（参见[[双噁唑啉配体]]），'''不对称Simmons–Smith反应'''却在1992年才得到首次应用。<ref>{{cite journal en| title = A catalytic enantioselective reaction using a C2-symmetric disulfonamide as a chiral ligand: cyclopropanation of allylic alcohols by the Et2Zn-CH2I2-disulfonamide system | journal = [[Tetrahedron Letters]] | volume = 33 | issue = 18 | year = 1992 | pages = 2575–2578 | author = Hideyo Takahashi, Masato Yoshioka, Masaji Ohno and Susumu Kobayashi | doi = 10.1016/S0040-4039(00)92246-9}}</ref> 在该反应中，[[肉桂醇]]与二乙基锌，二碘甲烷和一个手性的二[[磺酰胺]]在[[二氯甲烷]]中按照下式进行反应：

:[[File:AsymmetricSimmonsSmith.svg|600px|不对称Simmons-Smith反应]]

其中，[[羟基]]的存在是锚定锌（决定立体选择性）的前提条件。在另一个十分相似的反应中，用[[salen]]作配体，并且加入了[[路易斯酸]][[DIBAL]]，如下式所示：<ref>{{cite journal en| title = Asymmetric Simmons–Smith Reaction of Allylic Alcohols with Al Lewis Acid/N Lewis Base Bifunctional Al(Salalen) Catalyst | author =  Hiroaki Shitama and Tsutomu Katsuki | journal = [[Angew. Chem. Int. Ed.]] | year = 2008 | doi = 10.1002/anie.200705641 | volume = 47 | pages = 2450}}</ref>

:[[File:AsymmSimmonsSmith2008.svg|600px|不对称Simmons-Smith反应，由Shitama于2008年完成]]

== 参考文献 ==
{{reflist}}

== 外部链接 ==
{{Commonscat|Simmons-Smith reaction}}
*{{en}}[https://www.organic-chemistry.org/namedreactions/simmons-smith-reaction.shtm Simmons-Smith反应—organic-chemistry.org] {{Wayback|url=https://www.organic-chemistry.org/namedreactions/simmons-smith-reaction.shtm |date=20210423230628 }}

[[Category:加成反应]]
[[Category:人名反应]]
[[Category:碳-碳键形成反应]]
[[Category:三元环]]