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Regioselectivity and Stereochemistry of Hydroboration02:36

Regioselectivity and Stereochemistry of Hydroboration

A significant aspect of hydroboration–oxidation is the regio- and stereochemical outcome of the reaction.
Hydroboration proceeds in a concerted fashion with the attack of borane on the π bond, giving a cyclic four-centered transition state. The –BH2 group is bonded to the less substituted carbon and –H to the more substituted carbon. The concerted nature requires the simultaneous addition of –H and –BH2 across the same face of the alkene giving syn stereochemistry.
Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation02:47

Alkynes to Aldehydes and Ketones: Hydroboration-Oxidation

Introduction
One of the convenient methods for the preparation of aldehydes and ketones is via hydration of alkynes. Hydroboration-oxidation of alkynes is an indirect hydration reaction in which an alkyne is treated with borane followed by oxidation with alkaline peroxide to form an enol that rapidly converts into an aldehyde or a ketone. Terminal alkynes form aldehydes, whereas internal alkynes give ketones as the final product.
Hydroboration-Oxidation of Alkenes03:08

Hydroboration-Oxidation of Alkenes

In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation02:17

Reduction of Alkenes: Asymmetric Catalytic Hydrogenation

Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
Amides to Carboxylic Acids: Hydrolysis01:28

Amides to Carboxylic Acids: Hydrolysis

Amides can undergo either acid-catalyzed hydrolysis or base-promoted hydrolysis through a typical nucleophilic acyl substitution. Each hydrolysis requires severe conditions.
Acid-catalyzed hydrolysis:
Hydrolysis of amides under acidic conditions yields carboxylic acids. Since the reaction occurs slowly, hydrolysis requires the conditions of heat.
The mechanism begins with the protonation of the carbonyl oxygen by the acid catalyst. The protonation makes the amide carbonyl carbon more...
Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration02:34

Regioselectivity and Stereochemistry of Acid-Catalyzed Hydration

The rate of acid-catalyzed hydration of alkenes depends on the alkene's structure, as the presence of alkyl substituents at the double bond can significantly influence the rate.

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A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis
07:06

A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis

Published on: February 16, 2020

有效的胺导向的催化不对称的化.

Sean M Smith1, Nathan C Thacker, James M Takacs

  • 1Department of Chemistry, University of Nebraska-Lincoln, Lincoln, Nebraska 68588-0304, USA.

Journal of the American Chemical Society
|March 4, 2008
PubMed
概括

这项研究表明,高区域选择性和催化无环β,不和胺的高区域选择性和选择性催化氧化,使用性酸盐连接物和皮纳科尔波兰 (PinBH). 该方法有效地产生有价值的β-基胺,具有优异的反净度.

科学领域:

  • 有机化学 有机化学
  • 催化剂是一种催化剂.
  • 不对称的合成方法

背景情况:

  • 环状β,胺不和胺是多功能合成中间体.
  • 开发用于它们的功能化的酶选择性方法对于合成性分子至关重要.
  • 催化反应为选择性转换提供了强大的工具.

研究的目的:

  • 开发一种高度区域选择性和选择性催化非循环β,不和胺的氧化.
  • 为了确定这种转换的高效性配体和反应条件.
  • 为了证明有价值的β-胺胺产品的合成.

主要方法:

  • 使用 Rh ((nbd) 2BF4 和奇拉单或胺联体的催化化.
  • 基质范围的探索,包括非替代和三替代基.
  • 中介酸盐的氧化成β-基胺基.

主要成果:

  • 在化各种非循环β,不和胺的过程中,获得高区域选择性 (>95%) 和反选择性 (93-99% ee).
  • 确定了由BINOL衍生的光胺4和TADDOL衍生的酸5c作为高效的配体.
  • 证明了β-胺胺的高效合成,以 (S) -3-基赫萨诺酸胺为例,产量为80%和99% ee.
  • 发现N-phenyl amides和pinacolborane (PinBH) 分别比它们的类似物和catecholborane更有效.

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Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
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Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

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Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
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Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy

Published on: November 9, 2019

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A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis
07:06

A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis

Published on: February 16, 2020

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
06:46

Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate

Published on: June 21, 2017

Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy
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Versatile CO2 Transformations into Complex Products: A One-pot Two-step Strategy

Published on: November 9, 2019

  • 观察到有效的催化剂与适度的催化剂负载 (0.5mol%) 和温度在25-40°C之间.
  • 结论:

    • 已经建立了一个强大的,高效的催化化协议,用于非循环β,不和胺.
    • 开发的方法提供了对具有高区域和立体控制的酶体丰富的β-胺胺的访问.
    • 使用简单的性酸盐连接体为不对称合成提供了一种实用的方法.