Hydroboration and Diboration of Internal Alkynes Catalyzed by a Well-Defined Low-Valent Cobalt Catalyst

Ferrand, Laura; Lyu, Ye; Rivera-Hernández, Alejandro; Fallon, Brendan J.; Amatore, Muriel; Aubert, Corinne; Petit, Marc

doi:10.1055/s-0036-1588996

Cited by 29 publications

(19 citation statements)

References 14 publications

(9 reference statements)

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“…The first metal‐catalyzed diboration of alkynes was reported by Suzuki and Miyaura in 1993 using a Pt catalyst, and significantly improved Pt catalyst systems were reported by our group . During the last few years, Pd, Cu, Co, Fe, Zn, and metal‐free systems were reported for the diboration of alkynes, which provide practical and economic alternatives to the Pt‐catalyzed processes (Scheme b) . However, the availability of diverse multiborylalkenes is quite limited because of the lack of efficient and versatile synthetic methods.…”

Section: Methodsmentioning

confidence: 99%

Copper‐Catalyzed Triboration of Terminal Alkynes Using B₂pin₂: Efficient Synthesis of 1,1,2‐Triborylalkenes

et al. 2019

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We report herein the catalytic triboration of terminal alkynes with B2pin2 (bis(pinacolato)diboron) using readily available Cu(OAc)2 and PnBu3. Various 1,1,2‐triborylalkenes, a class of compounds that have been demonstrated to be potential matrix metalloproteinase (MMP‐2) inhibitors, were obtained directly in moderate to good yields. The process features mild reaction conditions, a broad substrate scope, and good functional group tolerance. This copper‐catalyzed reaction can be conducted on a gram scale to produce the corresponding 1,1,2‐triborylalkenes in modest yields. The utility of these products was demonstrated by further transformations of the C−B bonds to prepare gem‐dihaloborylalkenes (F, Cl, Br), monohaloborylalkenes (Cl, Br), and trans‐diaryldiborylalkenes, which serve as important synthons and have previously been challenging to prepare.

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Section: Methodsmentioning

confidence: 99%

Copper‐Catalyzed Triboration of Terminal Alkynes Using B₂pin₂: Efficient Synthesis of 1,1,2‐Triborylalkenes

et al. 2019

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“…The transition-metal-catalyzed diborylation of alkynes systematically displays 1,2-diborylalkenes with Z -stereochemistry in a selective manner, with a few exceptions that show mixtures of Z and E isomers or the formation of 1,1-diborylalkenes when the alkyne is terminal . For a M–BR 2 catalyst (Scheme ), the key intermediate for the formation of 1,2-diborylalkenes is a (R 2 B) 2 M{( Z )-β-C(R′)C(R″)BR 2 }-species, which can be formed by oxidative addition of diborane to a M{( Z )-β-C(R′)C(R″)BR 2 } compound and by insertion of the alkyne into a M–BR 2 bond of a M(BR 2 ) 3 derivative.…”

Section: Introductionmentioning

confidence: 99%

Rhodium-Mediated Dehydrogenative Borylation–Hydroborylation of Bis(alkyl)alkynes: Intermediates and Mechanism

et al. 2019

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Complex Rh(Bpin){κ 3 -P,O,P-[xant(P i Pr 2 ) 2 ]} (Bpin = pinacolboryl; xant(P i Pr 2 ) 2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) catalyzes the addition of B 2 pin 2 to 3-hexyne and 4octyne to give equimolecular mixtures of conjugated boryldienes and borylolefins, as a result of the addition of the B−B bond of the diborane to different molecules of alkynes and hydride transfer from one to the other. Both the dehydrogenative borylation and hydroborylation reactions form a catalytic cycle that has been deduced on the basis of stoichiometric studies. Complex Rh(Bpin){κ 3 -P,O,P-[xant(P i Pr 2 ) 2 ]} promotes the dehydrogenative borylation of alkynes by means of reactions of insertion of the alkyne into the Rh−B bond, Z−E isomerization of the β-borylalkenyl ligand of the resulting Rh−alkenyl species, and C γ −H bond activation of the alkyl substituent attached to the alkenyl C α atom. As a consequence of the formation of boryldienes, the monohydride RhH{κ 3 -P,O,P-[xant(P i Pr 2 ) 2 ]} is generated. The latter in a sequential manner reacts with the alkynes and the diborane to give the borylolefin hydroborylation products, via Rh−alkenyl intermediates, and regenerates the initial Rh−boryl compound. The latter also promotes stoichiometric cycles to prepare diboryl-2-olefins via allyl intermediates. In addition, the stoichiometric rhodiummediated formation of 1-boryl-2-olefins is shown.

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“…Suzuki und Miyaura demonstrierten 1993 die erste metallkatalysierte Diborierung von Alkinen unter Verwendung eines Pt‐Katalysators, woraufhin unsere Gruppe deutlich verbesserte Pt‐Katalysatoren entwickelte . In den letzten Jahren wurden Pd, Cu, Co, Fe, Zn und metallfreie Systeme auf die katalytische Aktivität gegenüber der Diborierung von Alkinen untersucht, welche eine praktische und kostengünstige Alternative zum Pt‐katalysierten System aufweisen (Schema b) . Die Zugänglichkeit verschiedener Multiborylalkene ist jedoch aufgrund des Fehlens an effizienten und vielseitigen Synthesemethoden sehr begrenzt.…”

Section: Methodsunclassified

Kupfer‐katalysierte Triborierung terminaler Alkine mit B₂pin₂: Effiziente Synthese von 1,1,2‐Triborylalkenen

et al. 2019

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Wir berichten über die katalytische Triborierung terminaler Alkine mit B2pin2 (Bis‐(pinakolato)‐dibor) unter Verwendung von einfach zugänglichem Cu(OAc)2 und PnBu3. Verschiedene 1,1,2‐Triborylalkene, eine Verbindungsklasse mit potentieller Funktion als Matrix‐Metallo‐Proteinase(MMP‐2)‐Inhibitor, werden direkt in mäßigen bis guten Ausbeuten erhalten. Das Verfahren zeichnet sich durch milde Reaktionsbedingungen, ein breites Substratspektrum und eine gute Verträglichkeit gegenüber funktionellen Gruppen aus. Diese Cu‐katalysierte Reaktion kann im Gramm‐Maßstab durchgeführt werden und liefert die entsprechenden 1,1,2‐Triborylalkene in mäßigen Ausbeuten. Die Verwendung solcher Verbindungen wird anhand weiterer Transformationen der C−B‐Bindungen zur Darstellung eines geminalen Dihalogenborylalkens (F, Cl, Br), eines Monohalogendiborylalkens (Cl, Br) und eines trans‐Diaryldiborylalkens demonstriert, welche bedeutende Synthesebausteine darstellen und bisher nur schwer zugänglich waren.

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Hydroboration and Diboration of Internal Alkynes Catalyzed by a Well-Defined Low-Valent Cobalt Catalyst

Abstract: The use of a simple well-defined low-valent cobalt(I) catalyst [HCo(PMe3)4] capable of performing the regio- and stereoselective hydroboration of internal alkynes is reported. Extension to the diboration of internal alkynes is also related using the same reaction conditions.

Cited by 29 publications

References 14 publications

Copper‐Catalyzed Triboration of Terminal Alkynes Using B₂pin₂: Efficient Synthesis of 1,1,2‐Triborylalkenes

Copper‐Catalyzed Triboration of Terminal Alkynes Using B₂pin₂: Efficient Synthesis of 1,1,2‐Triborylalkenes

Rhodium-Mediated Dehydrogenative Borylation–Hydroborylation of Bis(alkyl)alkynes: Intermediates and Mechanism

Kupfer‐katalysierte Triborierung terminaler Alkine mit B₂pin₂: Effiziente Synthese von 1,1,2‐Triborylalkenen

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Hydroboration and Diboration of Internal Alkynes Catalyzed by a Well-Defined Low-Valent Cobalt Catalyst

Abstract: The use of a simple well-defined low-valent cobalt(I) catalyst [HCo(PMe3)4] capable of performing the regio- and stereoselective hydroboration of internal alkynes is reported. Extension to the diboration of internal alkynes is also related using the same reaction conditions.

Cited by 29 publications

References 14 publications

Copper‐Catalyzed Triboration of Terminal Alkynes Using B2pin2: Efficient Synthesis of 1,1,2‐Triborylalkenes

Copper‐Catalyzed Triboration of Terminal Alkynes Using B2pin2: Efficient Synthesis of 1,1,2‐Triborylalkenes

Rhodium-Mediated Dehydrogenative Borylation–Hydroborylation of Bis(alkyl)alkynes: Intermediates and Mechanism

Kupfer‐katalysierte Triborierung terminaler Alkine mit B2pin2: Effiziente Synthese von 1,1,2‐Triborylalkenen

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Copper‐Catalyzed Triboration of Terminal Alkynes Using B₂pin₂: Efficient Synthesis of 1,1,2‐Triborylalkenes

Copper‐Catalyzed Triboration of Terminal Alkynes Using B₂pin₂: Efficient Synthesis of 1,1,2‐Triborylalkenes

Kupfer‐katalysierte Triborierung terminaler Alkine mit B₂pin₂: Effiziente Synthese von 1,1,2‐Triborylalkenen