(S)-4-叔丁基二甲基硅氧基-2-环戊酮 | 61305-36-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 中文名称: (S)-4-叔丁基二甲基硅氧基-2-环戊酮
• 中文别名: 4-叔丁基二甲硅氧基-2-环戊烯-1-酮；4-叔丁基二甲基硅氧基-2-环戊烯-1-酮
• 英文名称: (4S)-4-tert-butyldimethylsilyloxycyclopent-2-en-1-one
• 英文别名: (S)-4-((tert-butyldimethylsilyl)oxy)cyclopent-2-en-1-one；4-(S)-tert-butyldimethylsilyloxy cyclopent-2-enone；(4S)-(tert-butyldimethylsilyloxy)-cyclopent-2-en-1-one；4-(tert-butyldimethylsilyloxy)-2-cyclopentenone；4-(tert-butyldimethylsilyloxy)cyclopent-2-en-1-one；(S)-4-(tert-Butyldimethylsilyloxy)-2-cyclopentenone；(4S)-4-[tert-butyl(dimethyl)silyl]oxycyclopent-2-en-1-one
• CAS: 61305-36-0
• 化学式: C₁₁H₂₀O₂Si
• 分子量: 212.364
• InChiKey: DAPZSGCXUJECAI-SNVBAGLBSA-N

物化性质

• 稳定性/保质期：
  遵照规定使用和储存，则不会分解。

计算性质

• 辛醇/水分配系数(LogP)：
  2.91
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

安全信息

• 危险品标志：
  Xn
• 危险类别码：
  R20/21/22
• 安全说明：
  S36/37
• 储存条件：
  请将产品存放于阴凉干燥处。

SDS

Name:	(S)-4-Tert-Butyldimethylsilyloxy-2-Cyclopenten-1-one 95% (98% E.E.) Material Safety Data Sheet
Synonym:	None Known
CAS:	61305-36-0

Section 1 - Chemical Product MSDS Name:(S)-4-Tert-Butyldimethylsilyloxy-2-Cyclopenten-1-one 95% (98% E.E.) Material Safety Data Sheet
Synonym:None Known

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Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
61305-36-0	(S)-4-Tert-Butyldimethylsilyloxy-2-Cyc	95%	unlisted

Hazard Symbols: XN
Risk Phrases: 20/21/22

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Section 3 - HAZARDS IDENTIFICATION
EMERGENCY OVERVIEW
Harmful by inhalation, in contact with skin and if swallowed.The toxicological properties of this material have not been fully investigated.
Potential Health Effects
Eye:
May cause eye irritation.
Skin:
May cause skin irritation. Harmful if absorbed through the skin.
Ingestion:
Harmful if swallowed. May cause irritation of the digestive tract.
The toxicological properties of this substance have not been fully investigated.
Inhalation:
Harmful if inhaled. May cause respiratory tract irritation. The toxicological properties of this substance have not been fully investigated.
Chronic:
No information found.

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Section 4 - FIRST AID MEASURES
Eyes: Flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid.
Skin:
Get medical aid. Flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse.
Ingestion:
Never give anything by mouth to an unconscious person. Get medical aid. Do NOT induce vomiting. If conscious and alert, rinse mouth and drink 2-4 cupfuls of milk or water. Wash mouth out with water.
Inhalation:
Remove from exposure and move to fresh air immediately. If breathing is difficult, give oxygen. Get medical aid. Do NOT use mouth-to-mouth resuscitation. If breathing has ceased apply artificial respiration using oxygen and a suitable mechanical device such as a bag and a mask.
Notes to Physician:

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Section 5 - FIRE FIGHTING MEASURES
General Information:
As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion.
Extinguishing Media:
Use water spray, dry chemical, carbon dioxide, or chemical foam.

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Section 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Vacuum or sweep up material and place into a suitable disposal container. Clean up spills immediately, observing precautions in the Protective Equipment section. Avoid generating dusty conditions.
Provide ventilation.

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Section 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Use with adequate ventilation.
Minimize dust generation and accumulation. Avoid breathing dust, vapor, mist, or gas. Avoid contact with eyes, skin, and clothing.
Keep container tightly closed. Avoid ingestion and inhalation.
Storage:
Store in a cool, dry place. Store in a tightly closed container.

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Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Facilities storing or utilizing this material should be equipped with an eyewash facility and a safety shower. Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 61305-36-0: Personal Protective Equipment Eyes: Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or European Standard EN166.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to prevent skin exposure.
Respirators:
Follow the OSHA respirator regulations found in 29 CFR 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149 approved respirator if exposure limits are exceeded or if irritation or other symptoms are experienced.

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Section 9 - PHYSICAL AND CHEMICAL PROPERTIES

Physical State: Crystals
Color: yellow
Odor: Not available.
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: Not available.
Autoignition Temperature: Not available.
Flash Point: Not available.
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water:
Specific Gravity/Density:
Molecular Formula: C11H20O2Si
Molecular Weight: 212.36

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Section 10 - STABILITY AND REACTIVITY
Chemical Stability:
Not currently available.
Conditions to Avoid:
Dust generation.
Incompatibilities with Other Materials:
Oxidizing agents.
Hazardous Decomposition Products:
Nitrogen oxides, carbon monoxide, carbon dioxide, silicon dioxide.
Hazardous Polymerization: Has not been reported

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Section 11 - TOXICOLOGICAL INFORMATION
RTECS#:
CAS# 61305-36-0 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
(S)-4-Tert-Butyldimethylsilyloxy-2-Cyclopenten-1-one - Not listed by ACGIH, IARC, or NTP.

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Section 12 - ECOLOGICAL INFORMATION

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Section 13 - DISPOSAL CONSIDERATIONS
Dispose of in a manner consistent with federal, state, and local regulations.

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Section 14 - TRANSPORT INFORMATION

IATA
Not regulated as a hazardous material.
IMO
Not regulated as a hazardous material.
RID/ADR
Not regulated as a hazardous material.

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Section 15 - REGULATORY INFORMATION

European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: XN
Risk Phrases:
R 20/21/22 Harmful by inhalation, in contact with
skin and if swallowed.
Safety Phrases:
S 36/37 Wear suitable protective clothing and
gloves.
WGK (Water Danger/Protection)
CAS# 61305-36-0: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 61305-36-0 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 61305-36-0 is not listed on the TSCA inventory.
It is for research and development use only.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

反应信息

• 作为反应物：
  描述：

  (S)-4-叔丁基二甲基硅氧基-2-环戊酮 在 咪唑 、 双(乙腈)氯化钯(II) 、 sodium tetrahydroborate 、 正丁基锂 、 甲酸 、 platinum(II) oxide 、 四丁基氟化铵 、 氢气 、 Dimethylzinc 、 sodium 、 sodium naphthalenide 、 sodium cyanoborohydride 、 potassium carbonate 、 臭氧 、 三乙胺 、 三苯基膦 、 三氟乙酸 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 乙二醇二甲醚 、 乙醇 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 乙腈 为溶剂， -78.0~20.0 ℃ 、506.62 kPa 条件下， 反应 115.25h， 生成 (4R,4aS,6S,7S,7aR)-2,4,7-trimethyl-octahydro-1H-cyclopenta[c]pyridin-6-ol
  参考文献：
  名称：

  (-)-Incarvilline、(+)-Incarvine C 和 (-)-Incarvillateine 的全合成

  摘要：

  与天然对映体相对应的新单萜生物碱 (-)-incarvilline、(+)-incarvine C 和 (-)-incarvillateine 的首次全合成已经完成。这些天然产物的合成策略利用 6-epi-incarvilline 作为常见的前体，通过三组分偶联反应使用 (4S)-4-siloxy-2-cyclopenten-1-one 组装以构建适当的三取代的环戊酮，然后通过还原性 Heck 型反应闭环到顺式-全氢-2-吡啶骨架。此外，还研究了固态肉桂酸衍生物的拓扑化学控制 [2 + 2] 光二聚化，用于立体定向构建 1,2,3,4-四取代环丁烷环，作为获取 (-)-incarvillateine 的一种手段。

  DOI：

  10.1021/ja0401702
• 作为产物：
  描述：

  4-[(tert-butyldimethylsilyl)oxy]cyclopent-2-enone 在 Pancreatin 、 lithium aluminium tetrahydride 、 乙酸乙烯酯 、 sodium acetate 、 三乙胺 、 pyridinium chlorochromate 、 lithium iodide 作用下， 以 乙醚 、 二氯甲烷 、 甲基叔丁基醚 为溶剂， 反应 9.08h， 生成 (S)-4-叔丁基二甲基硅氧基-2-环戊酮
  参考文献：
  名称：

  通过仿生级联分子间迈克尔加成/环化反应合成（-）-哌啶酮和（-）-替尼吡酮的不对称总合成

  摘要：

  （-）-penicipyrone和（-）-tenuipyrone的第一批总合成是从已知的4-（（叔丁基二甲基甲硅烷基）氧基）环戊烯中以12步对映体选择性完成的，产率为11％，6步以28％的产率完成通过开发仿生双分子级联环化反应以分子间迈克尔加成/环-（螺-）缩酮化序列为代表的-2-烯酮。通过X射线晶体学分析和旋光度的比较进一步证实了哌替吡隆的相对，绝对立体化学和碳连接性。

  DOI：

  10.1021/ol303071t

文献信息

• Acylative Desymmetrization of Cyclic <i>meso</i>-1,3-Diols by Chiral DMAP Derivatives
  作者：Hiroki Mandai、Tsubasa Hironaka、Koichi Mitsudo、Seiji Suga

  DOI：10.1246/cl.200809

  日期：2021.3.5

  An efficient enantioselective acylative desymmetrization of cyclic meso-1,3-diols was developed by using a chiral DMAP derivative 1e having a 1,1′-binaphthyl unit. The reactions required only 0.5 m...

  通过使用具有 1,1'-联萘单元的手性 DMAP 衍生物 1e，开发了一种有效的环状内消旋 1,3-二醇的对映选择性酰化去对称化。反应只需要 0.5 m...
• Synthesis of Δ12,14-15-deoxy-PG-J1 methyl ester and epi-Δ12-15-deoxy-PG-J1
  作者：Mazhar Iqbal、Yingfa Li、Paul Evans

  DOI：10.1016/j.tet.2004.01.048

  日期：2004.3

  The synthesis of racemic Δ12,14-15-deoxy-PG-J1 is readily achieved in six steps employing as the key transformation a one-pot conjugate addition–Peterson olefination sequence using exo-2-trimethylsilyl-3a,4,7,7a-tetrahydro-4,7-methanoinden-1-one. Additionally a Noyori-type three-component coupling approach is employed for the synthesis of enantioenriched epi-Δ12-15-deoxy-PG-J1 from 4(S)-tert-butyl

  外消旋的Δ12,14 -15-deoxy-PG-J 1的合成很容易在六个步骤中完成，采用一锅共轭加成-Peterson烯化序列使用exo -2-三甲基甲硅烷基-3a，4,7作为关键转化，7a-四氢-4,7-蛋氨酸-1。另外被用于合成的野依型三组分偶联方法对映体富集的epi -Δ 12 -15脱氧PG-J 1从图4（小号） -叔-butyldimethylsilyloxycyclopent -2-烯酮。
• Catalytic Enantioselective Synthesis of 1,4‐Keto‐Alkenylboronate Esters and 1,4‐Dicarbonyls
  作者：Michael Z. Liang、Simon J. Meek

  DOI：10.1002/anie.201907757

  日期：2019.10

  catalytic enantioselective method for the synthesis of 1,4-keto-alkenylboronate esters by a rhodium-catalyzed conjugate addition pathway is disclosed. A variety of novel, bench-stable alkenyl gem-diboronate esters are synthesized. These easily accessible reagents react smoothly with a collection of cyclic α,β-unsaturated ketones, generating a new C-C bond and stereocenter. Products are isolated in up to

  公开了一种通过铑催化的共轭加成途径合成1，4-酮-烯基硼酸酯的催化对映选择性方法。合成了多种新颖的，长凳稳定的烯基宝石-二硼酸酯。这些易于获得的试剂可与一系列环状α，β-不饱和酮平稳反应，生成新的CC键和立体中心。以大于20：1的E / Z和大于99：1的产率分离出高达99％的产物。机理研究表明，金属转移的位点选择性和反应性取决于配体。该方法的实用性由对映体富集的环状1,4-二酮的克级合成，以及通过氢化，烯丙基化和异构化对产物进行立体选择性转化而突出。
• A Simple Zinc-Mediated Method for Selenium Addition to Michael Acceptors
  作者：Francesca Giulia Nacca、Bonifacio Monti、Eder João Lenardão、Paul Evans、Claudio Santi

  DOI：10.3390/molecules25092018

  日期：——

  biphasic Zn/HCl-based reducing system. Alkenes with a variety of electron-withdrawing groups were investigated in order to gauge the scope and limitations of the process. Results demonstrated that the addition to acyclic α,β-unsaturated ketones, aldehydes, esters amides, and acids was effectively achieved and that alkyl substituents at the reactive β-centre can be accommodated. Similarly, cyclic enones

  在这项工作中，我们将注意力集中在硒-迈克尔型反应上。这些是使用由二苯基二硒化物 1、1,2-双（3-苯基丙基）二硒化物 30 和受保护的硒代胱氨酸 31 原位生成的锌硒酸盐通过高效的双相 Zn/HCl 基还原系统进行的。研究了具有各种吸电子基团的烯烃，以衡量该过程的范围和局限性。结果表明，有效地实现了对无环 α,β-不饱和酮、醛、酯酰胺和酸的加成，并且可以容纳反应性 β-中心的烷基取代基。类似地，环烯酮进行有效的硒加成，相应的加合物以中等至良好的产率分离。乙烯基砜、α,β-不饱和腈、和查耳酮与这些反应条件不相容。循环实验表明，未反应的 Zn/HCl 还原系统可以有效地重复使用 7 个反应循环（在 7°循环循环时转化率为 91%）。
• Tandem Mukaiyama Michael–aldol reactions catalysed by samarium diiodide
  作者：Nicolas Giuseppone、Jacqueline Collin

  DOI：10.1016/s0040-4020(01)00902-4

  日期：2001.10

  Samarium diiodide is an efficient precatalyst for tandem Michael–aldol reactions, which allow the formation of two carbon–carbon bonds by successive additions of a ketene silyl acetal and an aldehyde on cyclic α,β-unsaturated ketones. The adducts are isolated as silyl ethers, in good yields, and in some cases with high diastereoselectivities when the reactions are performed at low temperatures. Comparative

  io二碘化物是串联迈克尔-羟醛反应的有效前催化剂，通过在环α，β-不饱和酮上连续添加乙烯酮甲硅烷基乙缩醛和醛，可以形成两个碳-碳键。加成物以高收率的形式分离为甲硅烷基醚，并且当在低温下进行反应时，在某些情况下具有高非对映选择性。提出了其他镧系元素碘化物对相同串联反应活性的比较研究。对于PGF的正式合成中的关键步骤2α已经通过串联迈克尔羟醛钐催化的序列来执行。