76385-38-1

Upstream product

• 591-87-7 Allyl acetate 
• 90-90-4 (4-bromophenyl)(phenyl)methanone 
• 53317-08-1 9-allyl-9-bora-bicyclo[3.3.1]nonane 
• 124643-34-1 p-benzoylphenyl triflate 
• 106-95-6 allyl bromide 
• 24850-33-7 allyltributylstanane 
• 6136-66-9 4-iodobenzophenone 
• 72824-04-5 2-Allyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 

Downstream Products

• 1334204-40-8 C₂₄H₂₉BO 
• 41882-77-3 4-(3-hydroxycarbonylpropyl)-benzophenone 

Relevant academic research and scientific papers

Cobalt-Catalyzed Allylic C(sp3)-H Carboxylation with CO2

Catalytic carboxylation of the allylic C(sp3)-H bond of terminal alkenes with CO2 was developed with the aid of a Co/Xantphos complex. A wide range of allylarenes and 1,4-dienes were successfully transformed into the linear styrylacetic acid and hexa-3,5-dienoic acid derivatives in moderate to high yields, with excellent regioselectivity. The carboxylation showed remarkable functional group tolerability, so that selective addition to CO2 occurred in the presence of other carbonyl groups such as amide, ester, and ketone. Since styrylacetic acid derivatives can be readily converted into optically active γ-butyrolactones through Sharpless asymmetric dihydroxylation, this allylic C(sp3)-H carboxylation showcases a facile synthesis of γ-butyrolactones from simple allylarenes via short steps.

Introduction of allyi and prenyl side-chains into aromatic systems by suzuki cross-coupling reactions

This paper reports some studies aiming at the developement of a general protocol useful for the synthesis of allyl- and prenylaromatic compounds. The first part deals with, the preparation of boron reagents like arylboronic acids and their pinacol esters as well as of pinacol allyl- and prenylboronates. The second part of the paper is devoted to the use of these boron reagents in Suzuki-Miyaura cross-coupling reactions leading to allylation and prenylation of aromatic compounds. Of the six methods studied, the most promising re-suits were obtained by using the Pd2(dba)3-catalyzed reactions of arylboronic acids with allyl and prenyl bromides, that lead to the products of cross coupling in high yields (average 87%), and the reactions of aryl trifluoroborates with allyl and prenyl bromides catalyzed by Pd(OAc)2 that lead to the products of coupling in all cases in high yields (average 82%).

Suzuki reactions with B-allyl-9-borabicyclo[3.3.1]nonane (B-allyl-9-BBN)

The mixture of borate complexes formed on treatment of B-allyl-9-BBN with KOMe readily undergoes Suzuki reactions in the presence of catalytic amounts of Pd(0) complexes, thus transferring their allyl moiety to aryl bromides, -iodides or -triflates.

PALLADIUM-CATALYZED CROSS-COUPLING REACTION: DIRECT ALLYLATION OF ARYL BROMIDES WITH ALLYL ACETATE

Various aryl bromides underwent a palladium-catalyzed cross-coupling reaction with allyl acetate in the presence of hexa-n-butylditin to give the allylated products in very high yields.

RADIKALISCHE REAKTIONSWEGE BEI THERMISCH INDUZIERTEN UMSETZUNGEN VON ZIRCONOCENKOMPLEXEN

The formation of products 2, 3 and 4(a-l) from both the reaction of εta2-bezophenone zirconocene 1 with alkyl halides and the thermolysis of the α-(Cp2ZrCl)-substituted benzhydrylmethylether 9, the latter proceeding with anchimeric assistance of the metal, can be understood assuming a stepwise reaction path through radical intermediates.The proposed intermediate transition-metal benzophenone ketyl 12 exhibits a reaction pattern differing from analogous main-group-metal ketyls.

REVERSAL OF THE BENZOPHENONE REACTIVITY UPON η2 -COMPLEXATION TO BIS( η5 -CYCLOPENTADIENYL)ZIRCONIUM

Reversal of the carbonyl activity of benzophenone, serving as electron donor in single-electron transfer processes and acting as a proton acceptor through the 'carbonyl'carbon atom, is observed upon η2 -complexation to zirconocene.