Copper(I)‐Catalyzed Enantioconvergent Borylation of Racemic Benzyl Chlorides Enabled by Quadrant‐by‐Quadrant Structure Modification of Chiral Bisphosphine Ligands

Iwamoto, Hiroaki; Endo, Kohei; Ozawa, Yasutomo; Watanabe, Yuta; Kubota, Koji; Imamoto, Tsuneo; Ito, Hajime

doi:10.1002/ange.201906011

Cited by 17 publications

(7 citation statements)

References 47 publications

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“…Indeed, during the preparation of this perspective, Ito disclosed rst examples on the asymmetric radical borylation of various racemic benzyl chlorides by using B 2 pin 2 in combination with a chiral Cu I complex (Scheme 31). 106 Considering the many top research teams that are worldwide active in this growing and competitive eld it is likely that many of the problems dened above will be solved in the near future.…”

Section: Discussionmentioning

confidence: 99%

New avenues for C–B bond formationviaradical intermediates

2019

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Section: Discussionmentioning

confidence: 99%

New avenues for C–B bond formationviaradical intermediates

2019

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“…In the second example, Ito and co-workers reported an enantioconvergent borylation reaction of racemic benzyl chlorides thought to proceed via a radical mechanism ( Figure 59 a). 224 Central to the success of the strategy was the use of a copper complex bearing a ligand belonging to the QuinoxP* family of bisphosphines ( Figure 59 b). These rigid bidentate phosphines are easily assembled and the nature of the substituents in each of the four ligand quadrants can be systematically varied.…”

Section: Carbon–heteroatom Bond-forming Reactionsmentioning

confidence: 99%

Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate

et al. 2020

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Enantioselective transition metal catalysis is an area very much at the forefront of contemporary synthetic research. The development of processes that enable the efficient synthesis of enantiopure compounds is of unquestionable importance to chemists working within the many diverse fields of the central science. Traditional approaches to solving this challenge have typically relied on leveraging repulsive steric interactions between chiral ligands and substrates in order to raise the energy of one of the diastereomeric transition states over the other. By contrast, this Review examines an alternative tactic in which a set of attractive noncovalent interactions operating between transition metal ligands and substrates are used to control enantioselectivity. Examples where this creative approach has been successfully applied to render fundamental synthetic processes enantioselective are presented and discussed. In many of the cases examined, the ligand scaffold has been carefully designed to accommodate these attractive interactions, while in others, the importance of the critical interactions was only elucidated in subsequent computational and mechanistic studies. Through an exploration and discussion of recent reports encompassing a wide range of reaction classes, we hope to inspire synthetic chemists to continue to develop asymmetric transformations based on this powerful concept.

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“…It should be noted that both enantiomers of t -Bu-BisP* could be conveniently prepared from 1,2-dichloroethane. 64 ) Among these ligands, AlkynylP*, 92 ) BulkyP*, 93 ) 5,8-TMS-QuinoxP*, 94 ) and 3H-QuinoxP* 95 – 97 ) have shown unique and remarkably high enantioselectivities in some transition-metal-catalyzed asymmetric transformations.…”

Section: Synthesis Of P-chiral Phosphine Ligandsmentioning

confidence: 99%