(benzenesulfonyl)methyllithium | 116511-95-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (benzenesulfonyl)methyllithium
• 英文别名: lithium methylphenylsulphone；lithiomethyl phenyl sulfone
• CAS: 116511-95-6
• 化学式: C₇H₇LiO₂S
• 分子量: 162.138
• InChiKey: RQYQDJQSQBTQLP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.73
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  26.4
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (benzenesulfonyl)methyllithium 生成 phenylsulfonyl-1 methyl-2 acetoxy-4 butene-2 Z
  参考文献：
  名称：

  合成砜-XXVI 1：合成醇和聚对苯二甲酸丙二醇酯，在4位合成壬烯酚

  摘要：

  DOI：

  10.1016/s0040-4020(01)91578-9
• 作为产物：
  描述：

  苯甲砜 在 正丁基锂 、 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 0.25h， 生成 (benzenesulfonyl)methyllithium
  参考文献：
  名称：

  含有磺酰基稳定碳负离子作为不可转移配体的混合高碳酸酯的反应

  摘要：

  在四氢呋喃中先用碘化亚铜（I）处理α-石棉砜，然后用1 mol处理。当量 烷基锂或格氏试剂的混合物会产生混合的纯铜[R'SO 2 CH 2 CuR] – M +（M = Li或MgX），是将R共轭加成烯酮并将酰氯中的氯化物取代成R的有效试剂产生酮（收率> 90％）。

  DOI：

  10.1039/c39820000358
• 作为试剂：
  描述：

  dimethyl 5,6,8,10-tetramethylheptalene-1,2-dicarboxylate 在 正丁基锂 、 (benzenesulfonyl)methyllithium 作用下， 以 四氢呋喃 为溶剂， 反应 74.0h， 生成 3-hydroxy-6,7,9,11-tetramethyl-2-(phenylsulfonyl)cyclopentaheptalene-1(1H)-one
  参考文献：
  名称：

  Formation of 3-Sulfonyl-Substituted Benzo[a]heptalene-2,4-diols from Heptalene-1,2-dicarboxylates and Lithiomethyl Phenyl Sulfones

  摘要：

  On treatment with 6 mol-equiv, of lithiomethyl phenyl sulfone at -78 degrees in THF, dimethyl 5,6,8,10-tetramethylhrptalene-1,2w-dicarboxylate (1b) gives, after raising the temperature to -10 degrees and addition of 6 mol-equiv. of BuLi; followed by further warming to ambient temperature, the corresponding 3-(phenyl- sulfonyl)benzo[a]haptalene-2,4-diol 2b in yields up to 65% (cf. Scheme 6 and Table 2),in contrast to its double-bond-shifted (DBS) isomer Ib which gave 2b in a yield of only 6% [1]. The bisanion [9](2-) of the cyclopenta[a]heptalen-1(1H)-one9 (cf. Fig. I),carrying a (phenylsulfonyl)methyl substituent at C(11b), seems to be a key intermediate on the reaction path to 2b, because 9 is transformed in high yield into 2b in the presence of 6 mol-equiv. of BuLi in the temperature range of -10 degrees to room temperature (cf Scheme 7). Heptalene-dicarboxylate 1'b was also transformed into benzo[a]heptalene-2,4-diols 2c-g by a number of lithiated methyl X-phenyl sulfones and BuLi (cf. Scheme 9 and Table 3).

  DOI：

  10.1002/(sici)1522-2675(19990310)82:3<372::aid-hlca372>3.0.co;2-h

文献信息

• Domino Elimination/Nucleophilic Addition in the Synthesis of Chiral Pyrrolidines
  作者：MariFe Flores、Pilar García-García、Narciso M. Garrido、Isidro S. Marcos、Francisca Sanz-González、David Díez

  DOI：10.1021/jo400873c

  日期：2013.7.19

  Polyhydroxylated pyrrolidines have been synthesized in a one-pot procedure by the addition of an organometallic reagent to isoxazolidines obtained by a 1,3-dipolar cycloaddition between nitrones and vinylsulfones. This method highlights sulfone reactivity and provides an easy approach for the preparation of chiral pyrrolidines using cyclic imines as key intermediates.

  多羟基化的吡咯烷是通过一锅法通过将有机金属试剂添加到异恶唑烷中而合成的，该异恶唑烷是通过在硝酮和乙烯基砜之间进行1,3-偶极环加成而获得的。该方法突出了砜的反应性，并为使用环状亚胺作为关键中间体制备手性吡咯烷提供了简便的方法。
• Enantiospecific synthesis and filed evaluation of four stereoisomers of 10,14-dimethyloctadec-1-ene, a sex pheromone component secreted by female moths of the apple leafminer
  作者：Tomonori Taguri、Katuhiko Yaginuma、Masanobu Yamamoto、Toru Fujii、Tetsu Ando

  DOI：10.1080/09168451.2014.905187

  日期：2014.5.4

  All four stereoisomers of 10,14-dimethyloctadec-1-ene, a sex pheromone component of the apple leafminer (Lyonetia prunifoliella: Lepidoptera), were synthesized starting from (R)- and (S)-propylene oxide by applying stereospecific inversion of chiral secondary tosylates as a key step. Field evaluation showed that male moths of the Japanese population were selectively attracted by the (10S,14S)-isomer

  10,14-二甲基十八烷基-1-烯（苹果除叶剂（Lyonetia prunifoliella：鳞翅目）的性信息素成分）的所有四种立体异构体都是通过（R）-和（S）-环氧丙烷通过应用手性立体定向转化而合成的次要甲苯磺酸盐是关键步骤。田间评估表明，日本种群的雄蛾被（10S，14S）异构体选择性吸引，而对映体未抑制其活性。
• Novel Approach to the Zaragozic Acids. Enantioselective Total Synthesis of 6,7-Dideoxysqualestatin H5
  作者：Satoru Naito、Maya Escobar、Philip R. Kym、Spiros Liras、Stephen F. Martin

  DOI：10.1021/jo011157s

  日期：2002.6.1

  The total synthesis of 6,7-dideoxysqualestatin H5 (3) has been completed by a concise approach that features the stereoselective intramolecular vinylogous aldol reaction of the furoic ester 25a to give 30 or its trimethylsilyl ether derivative 34, which possess the requisite absolute stereochemistry at C(3)-C(5) of 3. Compound 34 was reduced to the saturated bislactone 39, and the C(1) side chain subunit

  6,7-二脱氧角鲨烯抑制素H5（3）的总合成已通过一种简明的方法完成，该方法的特征是糠酸酯25a的立体选择性分子内乙烯基醛醇缩醛反应可生成30或其三甲基甲硅烷基醚衍生物34，该化合物具有必要的绝对立体化学结构。 C.（3）-C（5）为3。将化合物34还原为饱和双内酯39，并引入C（1）侧链亚基47，生成半缩醛48和相应的酮49的混合物。将该混合物与甲醇一起搅拌，发生缩酮化，得到50和螺环甲基乙缩醛51a，b的混合物。在50中氧化伯醇基团，然后对剩余的两个酯基进行皂化，得到3。
• Intramolecular diels-alder reactions of sulphonyl-substituted trienes
  作者：Donald Craig、Doris A. Fischer、Öznur Kemal、Andrew Marsh、Thomas Plessner、Alexandra M.Z. Slawin、David J. Williams

  DOI：10.1016/s0040-4020(01)96038-7

  日期：1991.5

  The synthesis and thermal intramolecular Diels-Alder reactions of a series of sulphonyl-substituted deca-, undeca- and dodecatrienes have been carried out. The stereoselectivities of these reactions are discussed, and methylation reactions of the bicyclic products are described.

  已经进行了一系列磺酰基取代的十-，十一-和十二碳烯的合成和分子内Diels-Alder热反应。讨论了这些反应的立体选择性，并描述了双环产物的甲基化反应。
• Stereocontrolled Total Synthesis of (−)-Kainic Acid. Regio- and Stereoselective Lithiation of Pyrrolidine Ring with the (+)-Sparteine Surrogate
  作者：Yasuhiro Morita、Hidetoshi Tokuyama、Tohru Fukuyama

  DOI：10.1021/ol051408+

  日期：2005.9.1

  [reaction: see text] A stereocontrolled total synthesis of (-)-kainic acid is described. cis-3,4-Disubstituted pyrrolidine ring was constructed by [3 + 2] cycloaddition of azomethine ylide with chiral butenolide. The crucial introduction of carboxyl group at the C-2 position was executed by regio- and stereoselective lithiation of the pyrrolidine ring in the presence of a (+)-sparteine surrogate followed

  [反应：见正文]描述了立体控制的（-）-海藻酸的全合成。顺式-3,4-二取代的吡咯烷环是通过偶氮甲酰内酯与手性丁烯内酯的[3 + 2]环加成而构建的。在（+）-天冬氨酸替代物的存在下，通过吡咯烷环的区域和立体选择性锂化来实现C-2位羧基的关键引入，然后用二氧化碳捕集。