(2S,4R)-5-methylhexane-2,4-diol

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2S,4R)-5-methylhexane-2,4-diol
• 化学式: C₇H₁₆O₂
• 分子量: 132.203
• InChiKey: YRDZJWZHGKDMBL-NKWVEPMBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  9
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  diisopropylsilanediyl bistriflate 、 (2S,4R)-5-methylhexane-2,4-diol 在 2,6-二甲基吡啶 作用下， 以 氘代氯仿 为溶剂， 以79%的产率得到trans-2,2,4-tri-isopropyl-6-methyl-1,3-dioxa-2-silacyclohexane
  参考文献：
  名称：

  Intramolecular hydrosilylations ii the -selective reduction of β-hydroxyketones

  摘要：

  DOI：

  10.1016/s0040-4020(01)86634-5
• 作为产物：
  描述：

  4-羟基-5-甲基-2-己酮 在 [N(methyl)2H2][(RuCl((S)-(phenyl)2P(binaphthyl)P(phenyl)2))2(μ-Cl)3] 、 氢气 作用下， 以 乙醇 为溶剂， 20.0 ℃ 、500.01 kPa 条件下， 反应 36.0h， 以88%的产率得到(2S,4R)-5-methylhexane-2,4-diol
  参考文献：
  名称：

  通过缩合/不对称氢化/酰化序列通过 β-Keto Weinreb 酰胺合成对映体纯 β-羟基酮

  摘要：

  获得对映体纯 β-羟基酮的既定途径是通过 β-酮酯的不对称氢化、酯/酰胺交换以及将所得 β-羟基酰胺用于有机金属化合物的酰化。我们通过证明在 [Me2NH2]+{[RuCl(S)-BINAP]2(µ-Cl)3}– (0.5 mol- %) 在室温/5 巴下。这些 Weinreb 酰胺是通过看似明显但前所未有的锂化 N-甲氧基-N-甲基乙酰胺与羧基氯化物的缩合反应制备的（产率 51-87%）。所得的 β-羟基 Weinreb 酰胺用于有机锂和格氏试剂的酰化。因此，他们得到了对映异构纯的 β-羟基酮（28 个例子）。这些化合物的选择产生了抗 1，

  DOI：

  10.1002/ejoc.201601202

文献信息

• The Zirconium Alkoxide-Catalyzed Aldol-Tishchenko Reaction of Ketone Aldols
  作者：Christoph Schneider、Markus Hansch、Timo Weide

  DOI：10.1002/chem.200400951

  日期：2005.1

  Evaluation of a broad range of metal alkoxides as catalysts and optimization of the reaction protocol led to a modified zirconium alkoxide catalyst with attenuated Lewis acidity and dichloromethane as solvent, which resulted in suppression of the undesired acyl migration to a large extent. Various ketone aldols have been prepared and subjected to the general process, giving rise to a broad range of differently

  酮醛醇作为烯醇当量的醛醇-季申科反应已被开发为一种有效的策略，可一步实现差异化的1,3-抗二醇单酯。热力学不稳定的酮醛醇醛容易地逆醛醇化，以原位产生推测的烯醇锆，然后通常以高收率和完全的1，3-抗非对映体进行醛醇-季申科反应。对各种金属醇盐作为催化剂的评估以及对反应方案的优化，导致了一种路易斯酸度降低且二氯甲烷为溶剂的改性醇锆氧化物催化剂，从而在很大程度上抑制了不希望的酰基迁移。制备了各种酮醛醇缩醛并进行了通用工艺，从而产生了范围广泛的不同取代的1，
• The application of difunctional organosilicon compounds to organic synthesis; 1,3-asymmetric induction in the reduction of β-hydroxy-ketones
  作者：Saeed Anwar、Anthony P. Davis

  DOI：10.1039/c39860000831

  日期：——

  A number of β-hydroxy-ketones were reduced to anti-1,3-diols with diastereoisomeric excesses exceeding 95%, by a method involving presumed intramolecular transfer of hydrogen from a silicon atom to the carbonyl carbon.

  通过一种涉及氢从硅原子到羰基碳的分子内转移的方法，许多β-羟基酮被还原为非对映异构体过量的抗-1,3-二醇。
• In search of open-chain 1,3-stereocontrol
  作者：Asun Barbero、David C. Blakemore、Ian Fleming、Robert N. Wesley

  DOI：10.1039/a607545b

  日期：——

  Methylation of methyl 4-phenylpentanoate 25 gives the diastereoisomers methyl (2RS,4SR )-2-methyl-4-phenylpentanoate 26 and methyl (2RS,4RS)- 2-methyl-4-phenylpentanoate 27 in a ratio of 44∶56. The aldehydes 3-dimethyl(phenyl)silylbutanal 28, 3-dimethyl(phenyl)silyl-3-phenylpropanal 32 and 3-dimethyl(phenyl)silyl-4-methylpentanal 36, each of which has a stereogenic centre on C-3 carrying a silyl group and successively also a methyl, a phenyl and an isopropyl group, react with a range of methyl, phenyl and isopropyl nucleophiles to give pairs of diastereoisomeric secondary alcohols 40–42, 47–49 and 54–56 having 1,3 related stereocentres. The same alcohols 43–45, 50–52 and 57–59 are also prepared by reduction of the corresponding ketones 29–31, 33–35 and 37–39 with a range of hydride reagents, and three of the ketones, 31, 35 and 39, react with phenyllithium to give mixtures of the tertiary alcohols 46, 53 and 60. The (E)- and (Z)-α,β-unsaturated methyl esters, 61, 62, 64, 65, 67 and 68, prepared from the same three aldehydes with methoxycarbonylmethyltriphenylphosphorane, react with the phenyldimethylsilyl-cuprate and -zincate reagents to give diastereoisomeric pairs of 1,3-disilylated esters. Likewise, the α,β-unsaturated dimethyl diesters, 63, 66 and 69, prepared from the same three aldehydes with dimethyl malonate, react with phenyldimethylsilyllithium and the corresponding cuprate and zincate reagents to give diastereoisomeric pairs of 1,3-disilylated diesters, and with various methyl and phenyl nucleophiles to give the corresponding pairs of diastereoisomeric diesters with stereogenic centres at C-3 and C-5. The relative stereochemistry of all but two of the products having 1,3-related stereocentres has been proved by silyl-to-hydroxy conversion using mercuric acetate and peracetic acid to give the corresponding alcohols or their derived lactones.An attempt to identify a purely steric rule by which it might be possible to predict which diastereoisomer would be the major product in each of these reactions was based on arguments about, and molecular mechanics calculations of, the lowest-energy conformations of the starting materials. The only rule that emerges is that ketones are regularly attacked in sense B, defined in the drawings 21 and 23, in a conformation that minimises the interaction between the group M on the stereogenic centre and the group R1 on the other side of the ketone, but even within this group of reactions, phenyl groups in either or both locations sometimes lead to anomalies.Krapcho reactions take place more rapidly and in higher yield using four equivalents of lithium chloride in place of the usual sodium chloride, and adding two equivalents of water to the DMSO.

  将 4-苯基戊酸甲酯 25 甲酯化，得到非对映异构体(2RS,4SR )-2-甲基-4-苯基戊酸甲酯 26 和(2RS,4RS)-2-甲基-4-苯基戊酸甲酯 27，比例为 44∶56。3-二甲基（苯基）硅基丁醛 28、3-二甲基（苯基）硅基-3-苯基丙醛 32 和 3-二甲基（苯基）硅基-4-甲基戊醛 36，每种醛的 C-3 上都有一个带有硅基的立体中心，并先后带有一个甲基、一个苯基和一个异丙基、与一系列的甲基、苯基和异丙基亲核物反应，得到一对非对映异构的仲醇 40-42、47-49 和 54-56，它们具有 1,3 个相关的立体中心。同样的醇 43-45、50-52 和 57-59 也可以通过相应的酮 29-31、33-35 和 37-39 与一系列氢化物试剂发生还原反应来制备，其中三个酮 31、35 和 39 与苯基锂发生反应，得到叔醇 46、53 和 60 的混合物。 (E)-和(Z)-α,β-不饱和甲基酯 61、62、64、65、67 和 68 由相同的三种醛与甲氧羰基甲基三苯基膦制备而成，它们与苯基二甲基硅琥珀酸酯试剂和锌酸试剂反应，得到非对映异构的 1,3-二硅烷化酯对。同样，由相同的三种醛与丙二酸二甲酯制备的 α、β-不饱和二甲基二酯 63、66 和 69 与苯基二甲基硅烷基锂及相应的铜酸盐和锌酸盐试剂发生反应，生成一对非对映异构的 1,3-二硅烷基二酯，与各种甲基和苯基亲核剂发生反应，生成相应的一对非对映异构的二酯，其立体中心位于 C-3 和 C-5。除了两种具有 1,3 相关立体中心的产物外，其他所有产物的相对立体化学性质都已通过使用乙酸巯基和过乙酸进行硅基-羟基转换而得到相应的醇或其衍生内酯得到证实。出现的唯一规则是，酮在图 21 和图 23 中定义的 B 意义上经常被攻击，其构象使立体中心上的基团 M 与酮另一侧的基团 R1 之间的相互作用最小，但即使在这组反应中，苯基在任一位置或两个位置有时也会导致异常。
• Ligand-Controlled, Norbornene-Mediated, Regio- and Diastereoselective Rhodium-Catalyzed Intramolecular Alkene Hydrosilylation Reactions
  作者：Yuanda Hua、Hiep H. Nguyen、William R. Scaggs、Junha Jeon

  DOI：10.1021/ol401464n

  日期：2013.7.5

  Ligand-controlled, norbornene-mediated, regio- and diastereoselective rhodium-catalyzed intramolecular alkene hydrosilylation of homoallyl silyl ethers (1) exploiting either BINAP or 1,6-bis(diphenylphosphino)hexane (dpph) has been developed. This method permits selective access to either trans-oxasilacyclopentanes (trans-2) or oxasilacyclohexanes (3) at will. A substoichiometric amount of norbornene

  已经开发了利用BINAP或1,6-双（二苯基膦基）己烷（dpph）进行配体控制，降冰片烯介导的区域和非对映体选择性铑催化的高烯丙基甲硅烷基醚（1）的分子内烯烃氢化硅烷化反应。该方法允许选择性地访问要么反-oxasilacyclopentanes（反式2）或oxasilacyclohexanes（3随意）。亚化学计量的降冰片烯显着提高了收率和选择性。讨论了降冰片烯介导的氢化物穿梭过程。
• Enzyme-Catalyzed Kinetic Resolution of 1,3-anti-Diol Monoesters – Efficient Preparation of Enantiomerically Highly Enriched and Unsymmetrically Substituted 1,3-anti-Diols
  作者：Florian Jakob、Christoph Schneider

  DOI：10.1002/ejoc.200700096

  日期：2007.6

  3-anti-diol monoesters which have been obtained through a zirconium-catalyzed aldol-Tishchenko reaction. The product 1,3-anti-diol diesters were formed in yields close to 50 % and >98 % ee. Separation from the unreactive enantiomers and subsequent hydrolysis furnished both enantiomers of unsymmetrically substituted 1,3-anti-diols in high optical purities. Alternatively, the kinetic resolution process can

  南极假丝酵母脂肪酶 B (CALB) 催化 1,3-抗二醇单酯的高度对映选择性乙酰化，该单酯是通过锆催化的羟醛-Tishchenko 反应获得的。产物1,3-反二醇二酯以接近50%和>98%ee的产率形成。从非反应性对映异构体中分离出来并随后水解，得到高光学纯度的不对称取代的 1,3-反二醇的两种对映异构体。或者，可以更快地对游离的 1,3-抗二醇进行动力学拆分过程，并获得同样好的结果。反应过程中缓慢的酰基迁移会略微破坏非反应性对映体的对映体过量。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)