Catalytic Homologation-Allylboration Sequence for Diastereo- and Enantioselective Synthesis of Densely Functionalized b-Fluorohydrins with Tertiary Fluoride Stereocenters

被引：9

作者：

Wang, Qiang ^{[1
]}

Eriksson, Lars ^{[2
]}

Szabo, Kalman J. ^{[1
]}

机构：

[1] Stockholm Univ, Dept Organ Chem, Stockholm, Sweden

[2] Stockholm Univ, Dept Mat & Environm Chem, Stockholm, Sweden

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2023年 / 62卷 / 19期

基金：

瑞典研究理事会;

关键词：

Allylboration; Homologation; Tertiary Fluoride; beta-Fluorohydrins; QUATERNARY STEREOCENTERS; FLUORINATION; ISOMERIZATION; CONSTRUCTION; ALDEHYDES; ACIDS;

D O I：

10.1002/anie.202301481

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Homologation of trisubstituted fluoroalkenes followed by allylboration of aldehyde, ketone and imine substrates is suitable for synthesis of beta-fluorohydrin and amine products. In the presence of (R)-iodo-BINOL catalyst enantioselectivities up to 99 % can be achieved by formation of a single stereoisomer with adjacent stereocenters, of which one is a tertiary C-F center.

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页数：6

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共 59 条

[1] Catalytic Enantioselective Synthesis of Allylic Boronates Bearing a Trisubstituted Alkenyl Fluoride and Related Derivatives [J].

Akiyama, Sota ;

Kubota, Koji ;

Mikus, Malte S. ;

Paioti, Paulo H. S. ;

Romiti, Filippo ;

Liu, Qinghe ;

Zhou, Yuebiao ;

Hoveyda, Amir H. ;

Ito, Hajime .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2019, 58 (35) :11998-12003

[2] Synthesis of Adjacent Quaternary Stereocenters by Catalytic Asymmetric Allylboration [J].

Alam, Rauful ;

Vollgraff, Tobias ;

Eriksson, Lars ;

Szabo, Kalman J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (35) :11262-11265

[3] Stereoselective allylboration of imines and indoles under mild conditions. An in situ E/Z isomerization of imines by allylboroxines [J].

Alam, Rauful ;

Das, Arindam ;

Huang, Genping ;

Eriksson, Lars ;

Himo, Fahmi ;

Szabo, Kalman J. .

CHEMICAL SCIENCE, 2014, 5 (07) :2732-2738

[4] Synthesis and Applications of α-Trifluoromethylated Alkylboron Compounds [J].

Argintaru, O. Andreea ;

Ryu, DaWeon ;

Aron, Ioana ;

Molander, Gary A. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2013, 52 (51) :13656-13660

[5] Asymmetric Fluorination Reactions promoted by Chiral Hydrogen Bonding-based Organocatalysts [J].

Auria-Luna, Fernando ;

Mohammadi, Somayeh ;

Divar, Masoumeh ;

Gimeno, M. Concepcion ;

Herrera, Raquel P. .

ADVANCED SYNTHESIS & CATALYSIS, 2020, 362 (23) :5275-5300

[6] Catalytic, Diastereoselective 1,2-Difluorination of Alkenes [J].

Banik, Steven M. ;

Medley, Jonathan William ;

Jacobsen, Eric N. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (15) :5000-5003

[7] Inverting Small Molecule-Protein Recognition by the Fluorine Gauche Effect: Selectivity Regulated by Multiple H→F Bioisosterism [J].

Bentler, Patrick ;

Bergander, Klaus ;

Daniliuc, Constantin G. ;

Mueck-Lichtenfeld, Christian ;

Jumde, Ravindra P. ;

Hirsch, Anna K. H. ;

Gilmour, Ryan .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2019, 58 (32) :10990-10994

[8] Brown Allylation: Application to the Synthesis of Natural Products [J].

Boiarska, Zlata ;

Braga, Tommaso ;

Silvani, Alessandra ;

Passarella, Daniele .

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2021, 2021 (22) :3214-3222

[9] A DFT study on the origin of the fluorine gauche effect in substituted fluoroethanes [J].

Buissonneaud, David Y. ;

van Mourik, Tanja ;

O'Hagan, David .

TETRAHEDRON, 2010, 66 (12) :2196-2202

[10] Transition-Metal-Catalyzed Monofluoroalkylation: Strategies for the Synthesis of Alkyl Fluorides by C-C Bond Formation [J].

Butcher, Trevor W. ;

Amberg, Willi M. ;

Hartwig, John F. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2022, 61 (07)

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