(S)-(cyclohept-1-en-1-ylmethyl)(methylimino)(phenyl)-l6-sulfanone | 167389-30-2

• 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: (S)-(cyclohept-1-en-1-ylmethyl)(methylimino)(phenyl)-l6-sulfanone
• CAS: 167389-30-2
• 化学式: C₁₅H₂₁NOS
• 分子量: 263.404
• InChiKey: DAKKXQXRBXYMQX-SFHVURJKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.03
• 重原子数：
  18.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  29.43
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (S)-(cyclohept-1-en-1-ylmethyl)(methylimino)(phenyl)-l6-sulfanone 在 咪唑 、 正丁基锂 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 26.5h， 生成 (3R,3aR)-3-(4-methoxyphenyl)-3,3a,4,5,6,7-hexahydro-1H-cyclohepta[c]furan
  参考文献：
  名称：

  通过甲硅烷氧基烯基氨基亚砜盐的α-消除和迁移环化不对称合成 2,3-二氢呋喃和不饱和双环四氢呋喃。手性双取代β-甲硅烷氧基亚烷基卡宾的生成和分子内O,Si-键插入

  摘要：

  用醛处理衍生自 β-甲基取代的无环烯丙基亚砜亚胺 13a 和 13b 的双（烯丙基亚砜亚胺）钛络合物，以高选择性得到相应的亚砜亚胺取代的高烯丙醇，其被分离为甲硅烷基醚 15a-h。亚砜亚胺 15a-h 的甲基化得到氨基亚砜盐 5a-h，在用 LiN(H)tBu 处理后，以高产率得到对映体和非对映体纯甲硅烷基取代的 2,3-二氢呋喃 4a-h。用 p-MeOC(6)H(4)CHO 处理衍生自环状烯丙基亚砜亚胺 17a、17b 和 ent-17c 的钛配合物，以高选择性提供相应的亚砜亚胺取代环状高烯丙醇，分离为甲硅烷基醚分别参见 18a、18b 和 ent-18c。亚砜亚胺 18a、18b、和 ent-18c 分别提供氨基锍盐 8a、8b 和 ent-8c，其用 LiN(H)t-Bu 处理得到对映和非对映异构纯稠合双环 2,3-二氢呋喃 6a、6b 和 ent- 6c，分别以良好的产量。提出 1-烯基氨基锍盐

  DOI：

  10.1021/ja030501v
• 作为产物：
  描述：

  (S)-1-[(N-methyl-S-phenylsulfonimidoyl)methyl]cycloheptanol 在 正丁基锂 、 三甲基氯硅烷 、 lithium methanolate 作用下， 生成 (S)-(cyclohept-1-en-1-ylmethyl)(methylimino)(phenyl)-l6-sulfanone
  参考文献：
  名称：

  Regio- and Enantioselective Substitution of Primary Endocyclic Allylic Sulfoximines with Organocopper and Organocuprate Reagents. The Importance of Iodide for the Allylic Substitution with Organocopper Compounds

  摘要：

  The endocyclic N-substituted allylic sulfoximines 17-20 and 26 were synthesized from the corresponding cycloalkanones and the various (S)-S-(lithiomethyl)-S-phenylsulfoximine in enantiomerically pure form in yields of 60-70% in a process involving the isomerization of the intermediate vinylic sulfoximines. Desilylation of 26 gave the parent N-H sulfoximine 27 from which the N-sulfonylsulfoximines 28 and 29 were prepared. The X-ray crystal structure of 28 was determined. The allylic sulfoximines 17-20 and 26-29 did not racemize or rearrange thermally to the corresponding allylic sulfinamides. Reaction of the allylic sulfoximines 18, 28, and 29 with the organocuprate reagents 2/LiI, 35/LiI, and 47/LiI led with alpha-selectivities of 92:8 to 99:1 to the endocyclic alkenes 39 in good to high yields. Reaction of 17-20, 28, and 29 with the organocopper reagents 5/LiI, 30/LiI, 31/LiI, 32/LiI, 33/LiI, 34/LiI, and 37/LiI in the presence of BF3 resulted in the formation of the exocyclic alkenes 38, 41, 43, and 45, respectively, in good to high yields with gamma-selectivities of 80:20 to 99:1. The sulfonimidoyl group imparts asymmetric induction to the substitution in the range of 27-90% ee. The (S)-sulfonimidoyl group leads to a preferential bond formation from the si side of the double bond. From the sulfoximines 18 and 26-29 the N-methylsulfoximine 18 and the N-tosylsulfoximine 28 showed the highest and lowest reactivity with the butylcopper reagent 32/LiI in the presence of BF3 respectively, while in the absence of BF3 only 29 reacted. The Lewis acid most likely serves to activate the N-methyl- and N-tosylsulfoximines or intermediates thereof through coordination at the sulfonimidoyl and sulfonyl group. Reaction of the sulfoximines 18 and 29 with pure Me(3)SiCH(2)Cu (34) revealed a strong rate acceleration by LiI and an even stronger one by Bu(4)NI. This points to the existence of a heteroleptic cuprate or a related compound as reactive species. In substitutions with the Yamamoto reagents RCu/MX/BF3, the halide is important and a reaction between RCu and BF3 does not have, at least in the case of allylic sulfoximines, to be invoked. In reactions of 17-20 besides the alkenes, the sulfinamide ent-4 was formed with an ee value of 97% in high yield with retention of configuration. The absolute configuration of the exocyclic alkenes 38, 41, and 45 was determined by ozonolysis to the corresponding cycloalkanones followed by their conversion to the corresponding lactones and/or CD measurement of the former.

  DOI：

  10.1021/ja00114a009

文献信息

• Asymmetric Synthesis of Cycloalkenyl and Alkenyloxiranes From Allylic Sulfoximines and Aldehydes and Application to Solid-Phase Synthesis
  作者：Hans-Joachim Gais、Gadamsetti S. Babu、Markus Günter、Parthasarathi Das

  DOI：10.1002/ejoc.200300726

  日期：2004.4

  chlorohydrins gave the corresponding enantio- and diastereomerically pure cis-configured cycloalkenyloxiranes in good overall yields, the alkenyl chlorohydrins afforded mixtures of enantiomerically pure trans and cis isomers in which the trans isomers dominated. The solution-phase synthesis was extended to the solid phase by the synthesis of an enantiomerically pure, polymer-bound allylic sulfoximine and its

  描述了从烯丙基亚砜亚胺和醛不对称合成环烯基和烯基环氧乙烷。用氯三（二乙氨基）钛对环状和无环烯丙基亚砜亚胺进行锂化和钛化，随后用醛处理，得到了对映和非对映异构纯、顺构型、亚砜亚胺取代的高烯丙醇。用氯甲酸氯乙酯处理亚砜亚胺取代的高烯丙醇导致亚砜亚胺基团被 Cl 原子轻易取代，形成相应的链烯基氯代醇。在环烯基衍生物的情况下，取代以高非对映选择性进行并保留构型，而在烯基衍生物的情况下，观察到具有构型反转的中等非对映选择性。虽然环烯基氯代醇的消除反应以良好的总产率得到相应的对映体和非对映体纯顺式构型环烯基环氧乙烷，但烯基氯代醇提供对映体纯反式和顺式异构体的混合物，其中反式异构体占主导地位。通过合成对映体纯的、聚合物结合的烯丙基亚砜亚胺并将其转化为烯基环氧乙烷，将溶液相合成扩展到固相。初步结果证明利用亚砜亚胺基团作为无痕手性接头的概念是可行的，并表明通过该路线固相不对称合成环烯基环氧乙烷应该是可能的。(©
• Asymmetric Synthesis of Substituted Homoallyl Alcohols, Halomethyl Tetrahydrofurans, and Chloro-amino Sulfones from Allyltitanium Sulfoximines and α-Hetero Aldehydes
  作者：A. Rajender、Hans-Joachim Gais

  DOI：10.1021/ol0627606

  日期：2007.2.1

  Asymmetric syntheses of the iodomethyl-substituted bicyclic tetrahydrofuran 22 and the chloro-amino sulfone 30 from the allylic sulfoximine 15 and the alpha-hetero aldehydes 2 and 23, respectively, are described. Further examples for the asymmetric synthesis of chloromethyl tetrahydrofurans and chloro-amino sulfones are given. The synthesis of 30 features as key step the stereoselective Cl-substitution

  描述了分别由烯丙基硫代肟基15和α-杂醛2和23不对称合成碘甲基取代的双环四氢呋喃22和氯氨基砜30。给出了不对称合成氯甲基四氢呋喃和氯氨基砜的其他例子。30个特征的合成是关键步骤，其羟基的立体选择性Cl-取代在相邻基团的作用下被氨基磺氧鎓基团转化为磺酰基。[反应：请参见文字]。
• Asymmetric Synthesis of Unsaturated, Fused Bicyclic Proline Analogues through Amino Alkylation of Cyclic Bis(allylsulfoximine)titanium Complexes and Migratory Cyclization of δ-Amino Alkenyl Aminosulfoxonium Salts
  作者：Stefan Koep、Hans-Joachim Gais、Gerhard Raabe

  DOI：10.1021/ja030324y

  日期：2003.10.1

  syn)-configured, delta-sulfoximine substituted, cyclic gamma,delta-unsaturated alpha-amino acid esters with high regio- and diastereoselectivities in good yields. Activation of the N-methyl sulfoximine group of these amino acid derivatives through methylation with Me(3)OBF(4) afforded in nearly quantitative yields the corresponding (dimethylamino)sulfoxonium salts. A novel migratory cyclization of these

  描述了由环状双（烯丙基亚砜亚胺）钛配合物和 N-叔丁基磺酰基亚氨基乙酯不对称合成新的 Delta(3a,4)-不饱和稠合双环脯氨酸类似物。用亚氨基酯处理对映体纯的五元、六元、七元和八元环状双（烯丙基亚砜亚胺）钛络合物，得到相应的 (E,syn)-和 (Z,syn)-构型的混合物，δ -亚砜亚胺取代的环状γ，δ-不饱和α-氨基酸酯，具有高产率和非对映选择性。这些氨基酸衍生物的 N-甲基亚砜亚胺基团通过甲基化与 Me(3)OBF(4) 活化，以几乎定量的方式提供相应的 (二甲氨基) 锍盐。这些盐与 DBU 的新型迁移环化通过异构化为相应的烯丙基（二甲氨基）锍盐和（二甲氨基）锍基团的分子内取代得到对映和非对映异构纯、双环、N-叔丁基磺酰基保护的脯氨酸类似物具有六元和八元不饱和碳环。烯基（二甲氨基）锍盐的环化与双键的构型无关。作为进一步的反应产物，以良好的收率获得≥99％ee的N，N-二甲基苯基亚
• Functionalized Chiral Vinyl Aminosulfoxonium Salts:  Asymmetric Synthesis and Application to the Synthesis of Enantiopure Unsaturated Prolines, β,γ-Dehydro Amino Acids, and Cyclopentanoid Keto Aminosulfoxonium Ylides
  作者：Shashi Kant Tiwari、Hans-Joachim Gais、Andreas Lindenmaier、Gadamsetti Surendra Babu、Gerhard Raabe、Leleti Rajender Reddy、Franz Köhler、Markus Günter、Stefan Koep、Vijaya Bhaskara Reddy Iska

  DOI：10.1021/ja061152i

  日期：2006.6.1

  Methylation of the enantiopure functionalized vinyl sulfoximines 5a-e and 14a-d followed by a F-ion or DBU-mediated isomerization of the vinyl aminosulfoxonium salts 7a-e and 15a-d, respectively, gave the allyl aminosulfoxonium salts 10a-e and 17a-d, respectively. A concomitant intramolecular substitution of the aminosulfoxonium group of 10a-e and 17a-d by the amino group afforded the unsaturated prolines 8a-e and 18a-d, respectively. The starting vinyl sulfoximines are accessible through a highly selective and stereo-complementary aminoalkylation of the corresponding sulfonimidoyl-substituted mono- and bis( allyl) titanium complexes with the imino ester 4. The vinyl aminosulfoxonium salts 34, 7a-d, and E-15c experienced upon treatment with the Cl- ion a migratory substitution with formation of the delta-chloro-beta,gamma-dehydro amino acids 36, E/Z-37a-d, and 38, respectively. A migratory substitution of the hydroxy-substituted vinyl aminosulfoxonium salts 46a and 46b furnished the delta-chloro allyl alcohols E/Z-48a and E-48b, respectively. A facile one-pot conversion of the vinyl sulfoximines 31b, 5c and 45a to the allyl chlorides 36, E/Z-37c and E/Z-48a, respectively, was achieved upon treatment with a chloroformiate. A tandem cyclization of the vinyl aminosulfoxonium salts 7b, Al-7b and 57 with LiN( H) tBu yielded the cyclopentanoid keto aminosulfoxonium ylides 54, Al-54, 59, 60 and 61, respectively. The structure of the tricyclic keto aminosulfoxonium ylide Al-54 has been determined by X-ray crystal structure analysis. Ab initio calculations and a NBO analysis of the tricyclic keto aminosulfoxonium ylide XXIII show a polar structure stabilized by electrostatic interactions between the ylidic C atom and both the carbonyl C atom and the S atom.