Efficient synthesis of chlorohydrins using ClCH2MgCl·LiCl

In this overview, we present our analysis of the future of organic synthesis in Brazil, a highly innovative and strategic area of research which underpins our social and economical progress. Several different topics (automation, catalysis, green chemistry, scalability, methodological studies and total syntheses) were considered to hold promise for the future advance of chemical sciences in Brazil. In order to put it in perspective, contributions from Brazilian laboratories were selected by the citations received and importance for the field and were benchmarked against some of the most important results disclosed by authors worldwide. The picture that emerged reveals a thriving area of research, with new generations of well-trained and productive chemists engaged particularly in the areas of green chemistry and catalysis. In order to fulfill the promise of delivering more efficient and sustainable processes, an integration of the academic and industrial research agendas is to be expected. On the other hand, academic research in automation of chemical processes, a well established topic of investigation in industrial settings, has just recently began in Brazil and more academic laboratories are lining up to contribute. All these areas of research are expected to enable the future development of the almost unchartered field of scalability.

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“…The use of mixed lithium-magnesium organometallic species have also been reported by the same group (Nishimura et al 2013, Batista et al 2015.…”

Section: Examples Of Large-scale Complex Synthesesmentioning

confidence: 70%

Organic Synthesis: New Vistas in the Brazilian Landscape

Pilli

Assis

2018

An. Acad. Bras. Ciênc.

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“…[3e] In 2013, Clososki et al ., explored the preparation of chloromethyl carbinol by using Li‐Mg carbenoid. [5a] Nevertheless, this efficient protocol to prepare chloromethyl carbinol does not generally extend to ketones. In 2015, Luisi et al ., reported chloromethyl carbinols preparation via lithium carbenoid by using flow microreactors.…”

Section: Introductionmentioning

confidence: 99%

A New Entry of Highly Selective and Nucleophilic BrH₂C‐ and ClH₂C‐Titanium Complexes for Carbonyl Coupling

2019

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The direct coupling of various aldehydes and ketones with CH2Br2 or CH2Cl2 promoted by TiCl4‐Mg bimetallic complex provides an extremely simple, practical, and efficient approach for the construction of bromomethyl or chloromethyl carbinols. The high chemoselectivity of this chemistry is illustrated by the TiCl4‐Mg‐promoted selective coupling of CH2Br2 or CH2Cl2 with an aldehyde in the presence of ketone and selective transfer of CH2Br or CH2Cl to saturated carbonyl moiety. This protocol is also suitable for sterically hindered and enolizable carbonyl compounds.

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“…Attempting the homologation with a more stable (but less nucleophilic) magnesium carbenoid (ClMgCH 2 Cl-LiCl) resulted in no transformation (entry 5). 19 It is worth observing the chemoselectivity of the process: no deleterious effect originated from the competitive Sn-Li exchange was noticed. As expected, changing ICH 2 Cl with ICH 2 Br -ceteris paribus -generated LiCH 2 Br, 20 which accomplished the homologation in comparable efficiency (entry 6).…”

mentioning

confidence: 99%

Homologation of halostannanes with carbenoids: a convenient and straightforward one-step access to α-functionalized organotin reagents

et al. 2018

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A direct, single synthetic homologative transformation of halostannanes into mono- or di-substituted methyl analogues is documented. Critical for the success of the operation is the excellent nucleophilicity of carbenoid-like methyllithium reagents (LiCHXY, X, Y = halogen, OR, and CN): by simply individuating the reagents' substitution pattern, the desired functionalized fragment is delivered to the electrophile. The wide scope of the protocol is evidenced also in the case of analogous halogermanium compounds. The tandem homologation-quenching with nucleophiles and the use of α-chloroallyllithium is also discussed.

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Efficient synthesis of chlorohydrins using ClCH2MgCl·LiCl

Cited by 23 publications

References 38 publications

Organic Synthesis: New Vistas in the Brazilian Landscape

Organic Synthesis: New Vistas in the Brazilian Landscape

A New Entry of Highly Selective and Nucleophilic BrH₂C‐ and ClH₂C‐Titanium Complexes for Carbonyl Coupling

Homologation of halostannanes with carbenoids: a convenient and straightforward one-step access to α-functionalized organotin reagents

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Efficient synthesis of chlorohydrins using ClCH2MgCl·LiCl

Cited by 23 publications

References 38 publications

Organic Synthesis: New Vistas in the Brazilian Landscape

Organic Synthesis: New Vistas in the Brazilian Landscape

A New Entry of Highly Selective and Nucleophilic BrH2C‐ and ClH2C‐Titanium Complexes for Carbonyl Coupling

Homologation of halostannanes with carbenoids: a convenient and straightforward one-step access to α-functionalized organotin reagents

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Product

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A New Entry of Highly Selective and Nucleophilic BrH₂C‐ and ClH₂C‐Titanium Complexes for Carbonyl Coupling