Simple Alkaline-Earth Metal Catalysts for Effective Alkene Hydrogenation

Angewandte Chemie
Heiko BauerSjoerd Harder

Abstract

Alkaline earth metal amides (AeN''2 : Ae=Ca, Sr, Ba, N''=N(SiMe3 )2 ) catalyze alkene hydrogenation (80-120 °C, 1-6 bar H2 , 1-10 mol % cat.), with the activity increasing with metal size. Various activated C=C bonds (styrene, p-MeO-styrene, α-Me-styrene, Ph2 C=CH2 , trans-stilbene, cyclohexadiene, 1-Ph-cyclohexene), semi-activated C=C bonds (Me3 SiCH=CH2 , norbornadiene), or non-activated (isolated) C=C bonds (norbornene, 4-vinylcyclohexene, 1-hexene) could be reduced. The results show that neutral Ca or Ba catalysts are active in the challenging hydrogenation of isolated double bonds. For activated alkenes (e.g. styrene), polymerization is fully suppressed due to fast protonation of the highly reactive benzyl intermediate by N''H (formed in the catalyst initiation). Using cyclohexadiene as the H source, the first Ae metal catalyzed H-transfer hydrogenation is reported. DFT calculations on styrene hydrogenation using CaN''2 show that styrene oligomerization competes with styrene hydrogenation. Calculations also show that protonation of the benzylcalcium intermediate with N''H is a low-energy escape route, thus avoiding oligomerization.

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Citations

Feb 1, 2019·Chemical Communications : Chem Comm·Isaiah R SpeightArnold L Rheingold
Jan 23, 2019·Angewandte Chemie·Heiko BauerSjoerd Harder
Apr 13, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Dafydd D L JonesCameron Jones
Jun 4, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Xianghui Shi, Jianhua Cheng
Jun 3, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Erwann Le CozYann Sarazin
Nov 30, 2019·Dalton Transactions : an International Journal of Inorganic Chemistry·Xianghui ShiJianhua Cheng
Nov 23, 2019·Chemistry : a European Journal·Erwann Le CozYann Sarazin
Feb 25, 2020·Angewandte Chemie·Peter M ChappleYann Sarazin
Feb 13, 2020·Angewandte Chemie·Ross F KobyTimothy P Hanusa
Jun 10, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Zhizhou LiuJianhua Cheng
Jul 22, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Louis J MorrisMichael S Hill
Jul 16, 2020·Chemistry : a European Journal·Gernot FrenkingNicole Holzmann
Sep 12, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Joanna HammoudYann Sarazin
Apr 27, 2019·Chemistry : a European Journal·Hanieh RoueindejiYann Sarazin
Nov 13, 2020·Angewandte Chemie·Philipp StegnerSjoerd Harder
Feb 18, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Philipp C StegnerSjoerd Harder
Jun 17, 2020·Inorganic Chemistry·Danny SchuhknechtJun Okuda
Jun 3, 2021·Chemical Communications : Chem Comm·Thomas HöllerhageJun Okuda
Jul 16, 2021·Accounts of Chemical Research·Mingfei Zhou, Gernot Frenking
Aug 28, 2021·Chemical Reviews·Matthew M D RoyEric Rivard
Dec 8, 2021·Journal of the American Chemical Society·Qiang DengShik Chi Edman Tsang

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