Direct Synthesis of Boron‐Protected Alkenyl‐ and Alkylborons via Copper‐Catalyzed Formal Hydroboration of Alkynes and Alkenes

Yoshida, Hiroto; Takemoto, Yumi; Takaki, Ken

doi:10.1002/ajoc.201402166

Cited by 54 publications

(17 citation statements)

References 56 publications

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“…Internal alkynes were also found to be hydroborated in regio-and stereoselective manners under the copper catalysis; alkyl(aryl)alkynes accepted the B(dan)-addition at the geminal position to the alkyl group in the presence of (Ph 3 P) 3 CuCl, whereas the reaction with (SIPr)CuCl resulted in the inverse regioselectivity (Scheme 9). 32 Furthermore, phenylacetylene and (trimethylsilyl)acetylene could be converted into the respective linear alkenylboron compounds with (Ph 3 P) 3 CuCl, verifying that the choice of ligands as well as the diminished boron-Lewis acidity is the key to achieving Markovnikov selectivity.…”

Section: -1 Monoborylation Including Addition To Unsaturated Carbon-carbon Bonds 3-1-1 Hydroboration and Related Reactionsmentioning

confidence: 91%

Recent Advances in Synthetic Transformations with Robust Yet Reactive B(dan) Moiety

Yoshida¹,

Li²

2021

HETEROCYCLES

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Recent advances in the direct B(dan)-installing reactions (dan = naphthalene-1,8-diaminato) into organic frameworks by utilizing (pin)B-B(dan) or H-B(dan) as a B(dan) source, and the direct cross-coupling of dan-substituted organoboron compounds therefrom are described. CONTENTS 1. Introduction 2. Synthesis of B(dan)-installing reagents 2-1. (pin)B-B(dan) 2-2. H-B(dan) 3. B(dan)-installing reactions with (pin)B-B(dan) 3-1. Monoborylation including addition to unsaturated carbon-carbon bonds 3-2. Monoborylation including substitution 3-3. Diborylation 4. B(dan)-installing reactions with H-B(dan) 4-1. Monoborylation including addition to unsaturated carbon-carbon bonds 4-2. Monoborylation including substitution 4-3. Diborylation 5. Direct cross-coupling with R-B(dan) 6. Conclusion Reaction conditions: (a) H2SO4 aq. or HCl aq., THF, rt; (b) Pd[P(tBu3)]2 (2 mol%), CsF, THF, 60 °C. (c) Pd[P(tBu)3]2 (2 mol%), NaOH aq., 1,4-dioxane, H2O, 60 °C, 4 h.

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Section: -1 Monoborylation Including Addition To Unsaturated Carbon-carbon Bonds 3-1-1 Hydroboration and Related Reactionsmentioning

confidence: 91%

Recent Advances in Synthetic Transformations with Robust Yet Reactive B(dan) Moiety

Yoshida¹,

Li²

2021

HETEROCYCLES

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“…As depicted in Scheme , perillyl alcohol or geraniol‐derived phosphate ( 2 l or 2 m ) could be transformed into the respective allyl−B(dan) ( 3 l or 3 m ) in 68% and 66% yield, showing that disubstitution at the γ‐position does not impede the reaction in the latter case. The distal C−C double bonds were not injured thoroughly (also in the case of 2 k ), despite the fact that simple aliphatic alkenes undergo the B(dan)‐installing reactions under copper catalysis ,,…”

Section: Methodsmentioning

confidence: 98%

Copper‐Catalyzed B(dan)‐Installing Allylic Borylation of Allylic Phosphates

2019

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γ-Selective B(dan)-installing allylic borylation was found to proceed efficaciously by the reaction of an unsymmetrical diboron, (pin)BÀ B (dan), with allylic phosphates under copper catalysis. The resulting allylÀ B(dan) was convertible into 1,3-, 1,2-, or 1,1-diborylalkanes with different boron-Lewis acidity by B(pin)-installing hydroboration, and its C(sp 3 )À B(dan) bond turned out to be preferentially transformed into a C(sp 3 )À N bond, leaving the B(pin) intact, despite its well-accepted inertness toward various transformations. Scheme 1. B(dan)-Installing Reactions with (pin)BÀ B(dan).

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“…Internal alkynes could also participate in the copper‐catalyzed hydroboration to give various alkenes bearing a B(dan) moiety in regio‐ and stereoselective manners; the B(dan)‐addition took place at a geminal position to an alkyl group of alkyl(aryl)alkynes in the presence of (Ph 3 P) 3 CuCl, whereas the use of SIPrCuCl as a catalyst resulted in the reverse regioselectivity (Scheme 23). [22] …”

Section: B(dan)‐installing Reactionsmentioning

confidence: 99%

Synthetic Chemistry with Lewis Acidity‐Diminished B(aam) and B(dan) Groups: Borylation Reactions and Direct Cross‐Couplings

Kamio

Yoshida

2020

Adv Synth Catal

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This review describes recent advances in the synthesis of anthranilamide/1,8‐diaminonaphthalene‐substituted organoboron compounds with diminished boron Lewis acidity via catalytic B(aam)‐ and B(dan)‐installing borylation reactions, which have attracted growing attention especially in the last five years owing to their unique reactivity, regioselectivity, and the outstanding stability toward air and moisture of organoboron compounds obtained therefrom. Direct Suzuki–Miyaura cross‐couplings with R–B(aam)/B(dan), which were believed to be wholly unreactive until recently, are also discussed.

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Direct Synthesis of Boron‐Protected Alkenyl‐ and Alkylborons via Copper‐Catalyzed Formal Hydroboration of Alkynes and Alkenes

Cited by 54 publications

References 56 publications

Recent Advances in Synthetic Transformations with Robust Yet Reactive B(dan) Moiety

Recent Advances in Synthetic Transformations with Robust Yet Reactive B(dan) Moiety

Copper‐Catalyzed B(dan)‐Installing Allylic Borylation of Allylic Phosphates

Synthetic Chemistry with Lewis Acidity‐Diminished B(aam) and B(dan) Groups: Borylation Reactions and Direct Cross‐Couplings

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