Catalytic Enantioselective Synthesis of <i>anti</i>‐Vicinal Silylboronates by Conjunctive Cross‐Coupling

Meng, Yu; Kong, Ziyin; Morken, James P.

doi:10.1002/ange.202000937

Cited by 14 publications

(1 citation statement)

References 60 publications

(23 reference statements)

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“…14 Notably, these are the first examples of dialkylarylsilylboranes that bear methoxy-(1u) or chloro groups (1v); such compounds cannot be directly prepared via the conventional method using an alkali metal. As the 4-MeO-C6H4Me2Si group is more reactive than the PhMe2Si group in Tamao-Flemming oxidations, 22 silylborane 1u will most likely find widespread applications in organic synthesis.…”

Section: Scheme 3 Discovery Of Rh-and Pt-based Catalytic Systems For the Si-h Borylation Of Trialkylsilanes A-cmentioning

confidence: 99%

General Synthesis of Trialkyl- and Dialkylarylsilylboranes: Versatile Silicon Nucleophiles in Organic Synthesis

et al. 2020

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Compared to carbon-based nucleophiles, the number of silicon-based nucleophiles that is currently available remains limited, which significantly hampers the structural diversity of synthetically accessible silicon-based molecules. Given the high synthetic utility and ease of handling of carbon-based boron nucleophiles, silicon-based boron nucleophiles, i.e., silylboranes, have received considerable interest in recent years as nucleophilic silylation reagents that are activated by transition-metal catalysts or bases. However, the range of practically accessible silylboranes remains limited. In particular, the preparation of sterically hindered and functionalized silylboranes remains a significant challenge. Here, we report the use of rhodium and platinum catalysts for the direct borylation of hydrosilanes with bis(pinacolato)diboron, which allows the synthesis of new trialkylsilylboranes that bear bulky alkyl groups and functional groups as well as new dialkylarylsilylboranes that are difficult to synthesize via conventional methods using alkali metals. We further demonstrate that these compounds can be used as silicon nucleophiles in organic transformations, which significantly expands the scope of synthetically accessible organosilicon compounds compared to previously reported methods. Thus, the present study can be expected to inspire the development of efficient methods for novel silicon-containing bioactive molecules and organic materials with desirable properties. We also report the first 11 B{ 1 H} and 29 Si{ 1 H} NMR spectroscopic evidence for the formation of i-Pr3SiLi generated by the reaction of i-Pr3Si-B(pin) with MeLi.

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Section: Scheme 3 Discovery Of Rh-and Pt-based Catalytic Systems For the Si-h Borylation Of Trialkylsilanes A-cmentioning

confidence: 99%

General Synthesis of Trialkyl- and Dialkylarylsilylboranes: Versatile Silicon Nucleophiles in Organic Synthesis

et al. 2020

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Synthesis of 1,3‐Bis‐(boryl)alkanes through Boronic Ester Induced Consecutive Double 1,2‐Migration

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2020

Angewandte Chemie

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A general and efficient approach for the preparation of 1,3‐bis‐(boryl)alkanes is introduced. It is shown that readily generated vinylboron ate complexes react with commercially available ICH2Bpin to valuable 1,3‐bis‐(boryl)alkanes. The introduced transformation, which is experimentally easy to conduct, shows broad substrate scope and high functional‐group tolerance. Mechanistic studies reveal that the reaction does not proceed via radical intermediates. Instead, an unprecedented boronic ester induced sequential bis‐1,2‐migration cascade is suggested.

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Stereospecific 1,2‐Migrations of Boronate Complexes Induced by Electrophiles

et al. 2020

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The stereospecific 1,2‐migration of boronate complexes is one of the most representative reactions in boron chemistry. This process has been used extensively to develop powerful methods for asymmetric synthesis, with applications spanning from pharmaceuticals to natural products. Typically, 1,2‐migration of boronate complexes is driven by displacement of an α‐leaving group, oxidation of an α‐boryl radical, or electrophilic activation of an alkenyl boronate complex. The aim of this article is to summarize the recent advances in the rapidly expanding field of electrophile‐induced stereospecific 1,2‐migration of groups from boron to sp2 and sp3 carbon centers. It will be shown that three different conceptual approaches can be utilized to enable the 1,2‐migration of boronate complexes: stereospecific Zweifel‐type reactions, catalytic conjunctive coupling reactions, and transition metal‐free sp2–sp3 couplings. A discussion of the reaction scope, mechanistic insights, and synthetic applications of the work described is also presented.

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Catalytic Enantioselective Synthesis of anti‐Vicinal Silylboronates by Conjunctive Cross‐Coupling

Cited by 14 publications

References 60 publications

General Synthesis of Trialkyl- and Dialkylarylsilylboranes: Versatile Silicon Nucleophiles in Organic Synthesis

General Synthesis of Trialkyl- and Dialkylarylsilylboranes: Versatile Silicon Nucleophiles in Organic Synthesis

Synthesis of 1,3‐Bis‐(boryl)alkanes through Boronic Ester Induced Consecutive Double 1,2‐Migration

Stereospecific 1,2‐Migrations of Boronate Complexes Induced by Electrophiles

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