123614-05-1Relevant articles and documents
Enantioselective catalytic allylation of carbonyl groups by umpolung of π-allyl palladium complexes
Zanoni, Giuseppe,Gladiali, Serafino,Marchetti, Alberto,Piccinini, Paolo,Tredici, Ilenia,Vidari, Giovanni
, p. 846 - 849 (2004)
Diethylzinc mediates the asymmetric allylation of aldehydes through Umpolung of a π-allyl palladium complex. An investigation of the palladium source and the chiral monophosphane ligands have shown that the leaving group has a dramatic effect on the enantioselectivity of the reaction. The procedure furnished products in satisfactory yields and up to 70% ee (see scheme).
Single-pot triple catalytic transformations based on coupling of in situ generated allyl boronates with in situ hydrolyzed acetals
Selander, Nicklas,Szabo, Kalman J.
, p. 3420 - 3422 (2008)
In situ hydrolyzed acetals were coupled with in situ generated allyl boronates in a one-pot procedure, affording regio- and stereodefined homoallyl alcohols, epoxides and amino alcohols. The Royal Society of Chemistry.
Synthesis of pinacol allylic boronic esters via olefin cross-metathesis between pinacol allylboronate and terminal or internal alkenes
Yamamoto,Takahashi,Miyaura
, p. 128 - 130 (2002)
The ruthenium-catalyzed olefin cross-metathesis between pinacol allylboronate, CH2=CHCH2B(O2C2Me4), and RCH=CH2 giving RCH=CHCH2B(O2C2Me4) was carried out in refluxing CH2Cl2 in the presence of an alkylidene-ruthenium complex (3 mol%).
Synthesis and application of chiral spiro phospholane ligand in Pd-catalyzed asymmetric allylation of aldehydes with allylic alcohols
Zhu, Shou-Fei,Yang, Yun,Wang, Li-Xin,Liu, Bin,Zhou, Qi-Lin
, p. 2333 - 2335 (2005)
(Chemical Equation Presented) A novel chiral monodentate spiro phenylphospholane ligand 4 was prepared from a readily accessible, enantiomerically pure 1,1′-spirobiindane-7,7′-diol in high yield. This ligand has proven to be efficient for Pd-catalyzed enantioselective allylation of aldehydes with allylic alcohols. Aromatic, heteroaromatic, and aliphatic aldehydes gave homoallylic alcohols in good enantioselectivities (up to 83% ee) and excellent anti diastereoselectivities (up to 99:1 dr).
Indium trichloride-promoted tin-mediated carbonyl allylation in water: High simple diastereo- and diastereofacial selectivity
Li, Xu-Ran,Loh, Teck-Peng
, p. 1535 - 1538 (1996)
Tin-mediated additions of allylic bromides to aldehydes and aldoses leads to adduct with high diastereo- and diastereofacial selectivity in the presence of indium trichloride in water.
Origin of the regio- and stereoselectivity in palladium-catalyzed electrophilic substitution via bis(allyl)palladium complexes
Wallner, Olov A.,Szabo, Kalman J.
, p. 4025 - 4030 (2003)
Palladium-catalyzed allylic substitution of aryl allyl chlorides with aromatic and heteroaromatic aldehydes was performed in the presence of hexamethylditin. This procedure involves palladium-catalyzed formation of transient allylstannanes followed by gen
SnCl2/PdCl2-mediated aldehyde allylation in fully aqueous media
Tan, Xiang-Hui,Hou, Yong-Quan,Shen, Bo,Liu, Lei,Guo, Qing-Xiang
, p. 5525 - 5528 (2004)
Catalyzed by PdCl2, SnCl2 can efficiently mediate the allylation of various aldehydes with allyl chloride or bromide, but not with allyl alcohol, in fully aqueous media. The yield of the reaction is very high (90-100%), and the reaction is operationally simple, environmental benign and easy to scale up.
Palladium-catalyzed electrophilic substitution via monoallylpalladium intermediates
Solin, Niclas,Kjellgren, Johan,Szabo, Kalman J.
, p. 3656 - 3658 (2003)
Nucleophilic rather than electrophilic reactivity is ascribed to the allyl moiety in (η1-allyl) palladium complexes such as 1, which are generated catalytically from allylstannanes and a palladium pincer complex and react smoothly with aldehydes.
Photocatalytic Umpolung Synthesis of Nucleophilic π-Allylcobalt Complexes for Allylation of Aldehydes
Shi, Caizhe,Li, Fusheng,Chen, Yuqing,Lin, Shuangjie,Hao, Erjun,Guo, Zhuowen,Wosqa, Urwa Tul,Zhang, Dandan,Shi, Lei
, p. 2992 - 2998 (2021/03/09)
The concept of "umpolung"reactivity of π-allylmetal complexes has been developed as a powerful method for the allylation of aldehydes. This paper describes the photocatalytic umpolung strategy for the synthesis of nucleophilic allylcobalt complexes through a single-electron-transfer (SET) process. This strategy enables the metallaphotoredox allylation of carbonyls with allyl acetate using organic N,N-diisopropylethylamine as the terminal reductant bypassing the use of a stoichiometric amount of metals. Ultraviolet-visible spectroscopy was used to monitor the redox changes of cobalt in the reaction.
Cobalt-Catalyzed Diastereo- And Enantioselective Reductive Allyl Additions to Aldehydes with Allylic Alcohol Derivatives via Allyl Radical Intermediates
Wang, Lei,Wang, Lifan,Li, Mingxia,Chong, Qinglei,Meng, Fanke
supporting information, p. 12755 - 12765 (2021/08/30)
Catalytic generation of ambiphilic π-allyl-metal complexes and their utility in enantioselective transformations constitutes a powerful approach for introduction of allyl groups to a molecule. Herein an unprecedented cobalt-catalyzed highly site-, diastereo-, and enantioselective protocol for stereoselective formation of nucleophilic allyl-Co(II) complexes followed by addition to aldehydes is presented. The reaction features diastereo- and enantioconvergent conversion of easily accessible allylic alcohol derivatives to diversified enantioenriched homoallylic alcohols with a remarkably broad scope of allyl groups that can be introduced. Mechanistic studies indicated that allyl radical intermediates were involved in this process. These new discoveries establish a new strategy for development of enantioselective transformations through capture of radicals by chiral Co complexes, pushing forward the frontier of Co complexes for enantioselective catalysis.
