(S)-3-hexyne-2-ol | 129364-62-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-3-hexyne-2-ol
• 英文别名: (S)-(-)-3-Hexyn-2-ol；(2S)-hex-3-yn-2-ol
• CAS: 129364-62-1
• 化学式: C₆H₁₀O
• 分子量: 98.1448
• InChiKey: IFCAMPHNVKBSTF-LURJTMIESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-3-hexyne-2-ol 在 正丁基锂 、 copper(I) bromide dimethylsulfide complex 、 三氟化硼乙醚 、 三正丁基氢锡 、 三乙胺 、 二异丙胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.17h， 生成 (2R,3R,4S)-1-(tert-Butyl-dimethyl-silanyloxy)-2,4-dimethyl-oct-5-yn-3-ol
  参考文献：
  名称：

  Synthesis of a syn,syn,syn,syn-Stereopentad Precursor of the Marine Sponge Polyketide Callystatin A

  摘要：

  A C13-22 syn,syn,syn,syn-stereopentad precursor of the cytotoxic polyketide callystatin A has been prepared. The synthesis involved BF3-promoted addition of the (M)-allenylstannane 28 to the alpha-methyl-beta-OTBS aldehyde 8 to afford the syn,syn adduct homopropargylic alcohol 29. Protection as the cyclic anisylidene acetal 31 and reduction of the acetylenic triple bond with Red-Al gave the (E)-allylic alcohol 32. This was subjected to Sharpless asymmetric epoxidation and subsequent treatment with an ethylcopper reagent to yield diol 34; hydrogenolysis of the derived tosylate 37 with LiBEt3H afforded 38. Acetal hydrogenolysis with DIBAl-H and oxidation yielded aldehyde 40 which was subjected to Horner-Emmons homologation to afford ester 41. This ester was converted to ester 44, an intermediate in the Kobayashi synthesis, with which it was found to be identical.

  DOI：

  10.1021/jo9902143
• 作为产物：
  描述：

  3-己炔-2-醇 在 sec-alkylsulfatase Pisa₁ 、 三氧化硫-三乙胺复合物 、 sodium hydride 、 对甲苯磺酸 作用下， 以 1,4-二氧六环 、 甲基叔丁基醚 、 水 、 paraffin oil 为溶剂， 反应 8.0h， 生成 (S)-3-hexyne-2-ol
  参考文献：
  名称：

  反向仲烷基硫酸酯酶Pisa1的底物谱

  摘要：

  使用一系列带有芳族，烯属和炔属部分的仲烷基硫酸酯对反相烷基硫酸酯酶Pisa1的底物谱进行了研究。对于带有与硫酸酯部分相邻的不同大小的基团的底物，获得了完美的对映选择性。通过使用二甲亚砜（DMSO）作为助溶剂，选择性可能会加倍。水解不稳定的苄基硫酸酯可通过引入吸电子取代基来充分稳定。总体而言，Pisa1似乎是的deracemisation一个非常有用的反相alkylsulfatase外消旋仲-醇通过 对其相应的硫酸酯进行酶水解，得到具有“反Kazlauskas”构型的同手性产物。

  DOI：

  10.1002/adsc.201100864

文献信息

• Catalytic Enantioselective Reduction of Ketones by a Chiral Gallium Complex and Catecholborane
  作者：Alan Ford、Simon Woodward

  DOI：10.1002/(sici)1521-3773(19990201)38:3<335::aid-anie335>3.0.co;2-t

  日期：1999.2.1

  Noyori's famous BINAL reagent Li[AlH(OEt)(BINOL dianion)] is formed by the combination of LiGaH4 , monothiobinaphthol (MTB), and catecholborane. With this mixture unsymmetrical ketones can be reduced in high enantioselectively. Un=unsaturated unit; R=alkyl.

  Noyori著名的BINAL试剂Li [AlH（OEt）（BINOL二价阴离子）]的催化活性形式是由LiGaH 4，单硫代二酚（MTB）和儿茶酚硼烷组成的。使用这种混合物，可以高对映选择性地还原不对称酮。Un =不饱和单位；R ＝烷基。
• Enantioselective Reduction of Prochiral Ketones by Catecholborane Catalysed by Chiral Group 13 Complexes
  作者：Alexander J. Blake、Anthony Cunningham、Alan Ford、Simon J. Teat、Simon Woodward

  DOI：10.1002/1521-3765(20001002)6:19<3586::aid-chem3586>3.0.co;2-s

  日期：2000.10.2

  asymmetric reduction of prochiral ketones, with catecholborane as the hydride source. Enantioface differentiation is on the basis of the steric requirements of the ketone substituents. Aryl/ n-alkyl ketones are reduced in 90-93% ee and RC(O)Me (e.g. R = iPr, cycloC6H11, tBu) in 60-72% ee. Other borane sources and alternative catalyst structures based on indium do not form enantioselective catalysts

  LiGaH4与S，O-螯合物2-羟基-2'-巯基-1,1'-联萘（MTBH2）结合以邻苯二酚硼烷为氢化物源，形成用于不对称还原前手性酮的活性催化剂。对映体的区别基于酮取代基的空间要求。在90-93％ee中还原芳基/正烷基酮，在60-72％ee中还原RC（O）Me（例如R = iPr，cycloC6H11，tBu）。其他硼烷源和基于铟的替代催化剂结构不形成对映选择性催化剂。
• Selective reductions. 46. Effect of the steric requirement at the 2-position of apopinene on chiral reductions. B-(iso-2-ethylapopinocampheyl)- and B-(iso-2-n-propylapopinocampheyl)-9-borabicyclo[3.3.1]nonanes as improved reagents for the chiral reduction of .alpha.,.beta.-acetylenic ketones and .alpha.-keto esters
  作者：Herbert C. Brown、P. Veeraraghavan Ramachandran、Steven A. Weissman、S. Swaminathan

  DOI：10.1021/jo00313a020

  日期：1990.12

  B-(Iso-2-ethylapopinocampheyl)-9-borabicyclo[3.3.1]nonane (Eapine-Borane, 7), and B-(Iso-2-n-propylapopinocampheyl)-9-borabicyclo[3.3.1]nonane (Prapine-Borane, 9), prepared via the hydroboration of 2-ethylapopinene (6) or 2-n-propylapopinene (8), respectively, with 9-borabicyclo[3.3.1]nonane, reduce prochiral alpha,beta-acetylenic ketones and alpha-keto esters to the corresponding alcohols with significantly higher optical induction than does Alpine-Borane (1). (-)-2-n-Propylapopinene was synthesized by treating nopyl tosylate with dimethyl cuprate prepared in situ from ethyllithium and cuprous iodide. (+)-2-n-Propylapopinene was synthesized by Schlosser metalation of (+)-alpha-pinene followed by treatment with ethyl iodide. 4-Phenyl-3-butyn-2-one was reduced to the corresponding propargylic alcohol in 89% ee and 96% ee by Eapine-Borane and Prapine-Borane, respectively, as compared to 82% ee with Alpine-Borane. Similar improved results were realized in the reduction of other acetylenic ketones by Eapine-Borane and Prapine-Borane. Similar improvements in the optical yields were realized in the reduction of alpha-keto esters by Eapine-Borane. For example, while Alpine-Borane produced methyl and ethyl lactate in 92% and 91% ee, respectively, Eapine-Borane gave these alcohols in 97% and 96% ee, respectively. Unfortunately, Prapine-Borane shows no improvement in percent ee for the reduction of alpha-keto esters. The increase in the percent ee realized is tentatively attributed to the increased steric requirements of the alkyl group at the 2-position of apopinene.
• Highly Enantioselective Propargylic Hydroxylations Catalyzed by Chloroperoxidase
  作者：Shanghui Hu、Lowell P. Hager

  DOI：10.1021/ja983612g

  日期：1999.2.1
• BROWN, HERBERT C.;VEERARAGHAVAN, RAMACHANDRAN P.;WEISSMAN, STEVEN A.;SWAM+, J. ORG. CHEM., 55,(1990) N6, C. 6328-6333
  作者：BROWN, HERBERT C.、VEERARAGHAVAN, RAMACHANDRAN P.、WEISSMAN, STEVEN A.、SWAM+

  DOI：——

  日期：——