Development of a flow method for the hydroboration/oxidation of olefins

Souto, José A.; Stockman, Robert A.; Ley, Steven V.

doi:10.1039/c5ob00170f

Cited by 18 publications

(22 citation statements)

References 54 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…8). 29 b-Pinene was used as a model substrate with a BH 3 complex in THF. After hydroboration in the first reactor, the intermediate is subjected to a stream of NaOH, H 2 O 2 , H 2 O, and EtOH to provide the alcohol in good yield in short residence times.…”

Section: Specific Examples Of Multi-step Transformationsmentioning

confidence: 99%

See 1 more Smart Citation

Multi-step continuous-flow synthesis

2017

View full text Add to dashboard Cite

Organic chemistry is continually evolving to improve the syntheses of value added and bioactive compounds. Through this progression, a concomitant advancement in laboratory technology has occurred. Many researchers now choose to mediate transformations in continuous-flow systems given the many benefits over round bottom flasks. Furthermore, reaction scale up is often less problematic as this is addressed at the inception of the science. Although single-step transformations in continuous-flow systems are common, multi-step transformations are more valuable. In these systems, molecular complexity is accrued through sequential transformations to a mobile scaffold, much like an in vitro version of Nature's polyketide synthases. Utilizing this methodology, multi-step continuous-flow systems have improved the syntheses of active pharmaceutical ingredients (APIs), natural products, and commodity chemicals. This Review details these advancements while highlighting the rapid progress, benefits, and diversification of this expanding field.

show abstract

Section: Specific Examples Of Multi-step Transformationsmentioning

confidence: 99%

“…8 Continuous-flow hydroboration and subsequent oxidation through a two-step process. 29 In this example, 13 compounds were synthesized in good to excellent yields. Fig.…”

Section: Facilitating Natural Products Synthesismentioning

confidence: 99%

Multi-step continuous-flow synthesis

2017

View full text Add to dashboard Cite

show abstract

“…Trifluoromethanesulfonic acid-catalyzed diacetoxylation of alkenes with peracetic acid generated in situ from acetic anhydride and H2O2 in a microreactor. 273 A continuous-flow protocol for the two-step hydroboration/oxidation of olefins was developed by Souto et al 274 In the first step, the olefin was hydroborated by BH3.THF in a PFA capillary microreactor (1 mm ID, 2 mL). Next, the reaction stream was merged with a basic H2O2 solution to oxidize the boron intermediate to the corresponding alcohol.…”

Section: Oxidation Processes In Flow By Means Of Hydrogen Peroxidementioning

confidence: 99%

Liquid phase oxidation chemistry in continuous-flow microreactors

et al. 2016

View full text Add to dashboard Cite

Continuous-flow liquid phase oxidation chemistry in microreactors receives a lot of attention as the reactor provides enhanced heat and mass transfer characteristics, safe use of hazardous oxidants, high interfacial areas, and scale-up potential. In this review, an up-to-date overview of both technological and chemical aspects of liquid phase oxidation chemistry in continuous-flow microreactors is given. A description of mass and heat transfer phenomena is provided and fundamental principles are deduced which can be used to make a judicious choice for a suitable reactor. In addition, the safety aspects of continuous-flow technology are discussed. Next, oxidation chemistry in flow is discussed, including the use of oxygen, hydrogen peroxide, ozone and other oxidants in flow. Finally, the scale-up potential for continuous-flow reactors is described.

show abstract

“…Unfortunately, many of these reactions require reagents that are not commercially available or are not economically viable to use on industrial-scale levels. While Souto et al have developed a flow method for the hydroboration/oxidation of olefins, their method has only been applied to β-pinene, 1-hexene and 1-octene [10]. Clay and Vedejs have shown that pyridine borane activated by iodine in dichloromethane can be used to hydroborate 1-dodecene with high yield at room temperature [13].…”

Section: Introductionmentioning

confidence: 99%

“…During the past two decades, numerous approaches to the synthesis of higher molecular weight linear primary alcohols have been published. Hydroborations employing borane-THF or borane-DMS [9,10], chloroborane adducts [11] and transition metal catalyzed hydroboration reagents [12] have generated significant interest in the field. Unfortunately, many of these reactions require reagents that are not commercially available or are not economically viable to use on industrial-scale levels.…”

Section: Introductionmentioning

confidence: 99%

A Simple, Cost-effective Synthesis of Industrially Important Long Chain Primary Alcohols

Milofsky¹,

Hurley²,

Heston³

et al. 2017

Open Chem. J.

View full text Add to dashboard Cite

Abstract:The hydroboration oxidation of high molecular weight α-olefins (C 18 -C 30+ ) with sodium malonyloxyborohydride (SMB) to generate the corresponding primary alcohols is described. α-Olefins undergo hydroboration upon treatment with sodium borohydride (NaBH 4 ) and malonic acid, methyl malonic acid, dimethyl malonic acid or ethyl malonic acid, and a straightforward oxidation of these alkyl boranes yields the anti-Markovnikov primary alcohols. Following recrystallization in n-hexane, n-octane, n-decane or ndodecane, the target alcohols were isolated in high purity (>99%). The use of SMB and its derivatives will allow synthesis of larger (C 18 -C 30+ ) primary alcohols on an industrial scale without the costs and hazards of current methods.

show abstract

Development of a flow method for the hydroboration/oxidation of olefins

Cited by 18 publications

References 54 publications

Multi-step continuous-flow synthesis

Multi-step continuous-flow synthesis

Liquid phase oxidation chemistry in continuous-flow microreactors

A Simple, Cost-effective Synthesis of Industrially Important Long Chain Primary Alcohols

Contact Info

Product

Resources

About