Synthesis of γ‐Boryl‐Substituted Homoallylic Alcohols with <i>anti</i> Stereochemistry Based on a Double‐Bond Transposition

Miura, Tomoya; Nakahashi, Junki; Sasatsu, Takanori; Murakami, Masahiro

doi:10.1002/anie.201811205

Cited by 28 publications

(14 citation statements)

References 62 publications

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“…Although many synthetic methods utilize transformations of C–B bonds, the development of polyborylated reagents would enable greater structural diversity, an important objective . Therefore, over the past decade, much effort has been expended to synthesize new functionalized classes of polyboronates, which have been shown to be excellent building blocks for the modular construction of new compounds. − …”

Section: Introductionmentioning

confidence: 99%

Stereoselective Diels–Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers

et al. 2021

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Although gem -diborylalkenes are known to be among the most valuable reagents in modern organic synthesis, providing a rapid access to a wide array of transformations, including the construction of C–C and C-heteroatom bonds, their use as dienophile-reactive groups has been rare. Herein we report the Diels–Alder (DA) reaction of (unsymmetrical) gem -diborylalkenes. These reactions provide a general and efficient method for the stereoselective conversion of gem -diborylalkenes to rapidly access 1,1-bisborylcyclohexenes. Using the same DA reaction manifold with borylated-dienes and gem- diborylalkenes, we also developed a concise, highly regioselective synthesis of 1,1,2-tris- and 1,1,3,4-tetrakis(boronates)cyclohexenes, a family of compounds that currently lack efficient synthetic access. Furthermore, DFT calculations provided insight into the underlying factors that control the chemo-, regio-, and stereoselectivity of these DA reactions. This method also provides stereodivergent syntheses of gem- diborylnorbornenes. The utility of the gem- diborylnorbornene building blocks was demonstrated by ring-opening metathesis polymerization (ROMP), providing a highly modular approach to the first synthesis of the gem- diboron-based polymers. Additionally, these polymers have been successfully submitted to postpolymerization modification reactions. Given its simplicity and versatility, we believe that this novel DA and ROMP approach holds great promise for organoboron synthesis as well as organoboron-based polymers and that it will result in more novel transformations in both academic and industrial research.

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Section: Introductionmentioning

confidence: 99%

Stereoselective Diels–Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers

et al. 2021

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“…The generated allylic boron species immediately adds to aldehydes, where a high enantioselectivity is induced by the chiral phosphoric acid . Homoallylic alcohols functionalized with silicon and boron at the γ and δ positions can be synthesized from 1‐boryl‐2‐silylalk‐1‐enes, 1,2‐di(boryl)alk‐1‐enes, and 1,1‐di(boryl)alk‐3‐enes . We next examined the use of 1,1‐di(boryl)alk‐1‐enes as the precursor (alkenyl)boron compounds, which would give rise to δ‐boryl‐substituted homoallylic alcohols.…”

Section: Figurementioning

confidence: 99%

Diastereo‐ and Enantioselective Synthesis of (E)‐δ‐Boryl‐Substituted anti‐Homoallylic Alcohols in Two Steps from Terminal Alkynes

2019

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We report the highly diastereo-and enantioselective preparation of (E)-d-boryl-substituted anti-homoallylic alcohols in two steps from terminal alkynes.T his method consists of ac obalt(II)-catalyzed 1,1-diboration reaction of terminal alkynes with B 2 pin 2 and ap alladium(I)-mediated asymmetric allylation reaction of the resulting 1,1-di(boryl)alk-1-enes with aldehydes in the presence of achiral phosphoric acid. Propyne, which is produced as the byproduct during petroleum refining, could be used as the starting material to construct homoallylic alcohols that are otherwise difficult to synthesize with high stereocontrol.

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“…Murakami entwickelt neue, interessante und nützliche organische Umwandlungen, zurzeit mit einem Schwerpunkt auf photochemischer organischer Synthese. Seine Gruppe berichtete in einer Angewandte‐Chemie ‐Zuschrift über die Synthese γ‐borylierter Homoallylalkohole …”

Section: Ausgezeichnet …unclassified

Cope und Cope Scholar Awards 2019

2019

Angewandte Chemie

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Synthesis of γ‐Boryl‐Substituted Homoallylic Alcohols with anti Stereochemistry Based on a Double‐Bond Transposition

Cited by 28 publications

References 62 publications

Stereoselective Diels–Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers

Stereoselective Diels–Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers

Diastereo‐ and Enantioselective Synthesis of (E)‐δ‐Boryl‐Substituted anti‐Homoallylic Alcohols in Two Steps from Terminal Alkynes

Cope und Cope Scholar Awards 2019

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