Triply Selective & Sequential Diversification at Csp3: Expansion of Alkyl Germane Reactivity for C-C & C-Heteroatom Bond Formation

被引：9

作者：

Ahrweiler, Eric ^{[1
]}

Schoetz, Markus D. ^{[1
]}

Singh, Gurdeep ^{[1
]}

Bindschaedler, Quentin P. ^{[1
]}

Sorroche, Alba ^{[1
]}

Schoenebeck, Franziska ^{[1
]}

机构：

[1] Rhein Westfal TH Aachen, Inst Organ Chem, Landoltweg 1, D-52074 Aachen, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2024年 / 63卷 / 16期

基金：

欧盟地平线“2020”; 欧洲研究理事会;

关键词：

site-selectivity; alkyl germane; modularity; catalysis; radical chemistry; photochemistry; TERTIARY BORONIC ESTERS; REDOX-ACTIVE ESTERS; CONSTRUCTION; SECONDARY; ACCESS; FUNCTIONALIZATION; HALIDES; OXYGEN;

D O I：

10.1002/anie.202401545

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

We report the triply selective and sequential diversification of a single C-sp(3) carbon carrying Cl, Bpin and GeEt3 for the modular and programmable construction of sp(3)-rich molecules. Various functionalizations of C-sp(3)-Cl and C-sp(3)-BPin (e.g. alkylation, arylation, homologation, amination, hydroxylation) were tolerated by the C-sp(3)-GeEt3 group. Moreover, the methodological repertoire of alkyl germane functionalization was significantly expanded beyond the hitherto known Giese addition and arylation to alkynylation, alkenylation, cyanation, halogenation, azidation, C-S bond formation as well as the first demonstration of stereo-selective functionalization of a C-sp(3)-[Ge] bond.

引用

页数：6

共 70 条

[1] Site-selective Suzuki-Miyaura coupling of heteroaryl halides - understanding the trends for pharmaceutically important classes [J].

Almond-Thynne, Joshua ;

Blakemore, David C. ;

Pryde, David C. ;

Spivey, Alan C. .

CHEMICAL SCIENCE, 2017, 8 (01) :40-62

[2]

Ball P., 2015, Navigating chemical, space can be found under

[3] Automated iterative Csp3-C bond formation [J].

Blair, Daniel J. ;

Chitti, Sriyankari ;

Trobe, Melanie ;

Kostyra, David M. ;

Haley, Hannah M. S. ;

Hansen, Richard L. ;

Ballmer, Steve G. ;

Woods, Toby J. ;

Wang, Wesley ;

Mubayi, Vikram ;

Schmidt, Michael J. ;

Pipal, Robert W. ;

Morehouse, Greg F. ;

Ray, Andrea M. E. Palazzolo ;

Gray, Danielle L. ;

Gill, Adrian L. ;

Burke, Martin D. .

NATURE, 2022, 604 (7904) :92-+

[4]

Bonet A, 2014, NAT CHEM, V6, P584, DOI [10.1038/NCHEM.1971, 10.1038/nchem.1971]

[5]

Bootwicha T, 2017, NAT CHEM, V9, P896, DOI [10.1038/nchem.2757, 10.1038/NCHEM.2757]

[6] Emergent synthetic methods for the modular advancement of sp3-rich fragments [J].

Caplin, Max J. ;

Foley, Daniel J. .

CHEMICAL SCIENCE, 2021, 12 (13) :4646-4660

[7] Exploring benzylic gem-C(sp3)-boron-silicon and boron-tin centers as a synthetic platform [J].

Chen, Wei W. ;

Fernandez, Nahiane Pipaon ;

Baranda, Marta Diaz ;

Cunillera, Anton ;

Rodriguez, Laura G. ;

Shafir, Alexandr ;

Cuenca, Ana B. .

CHEMICAL SCIENCE, 2021, 12 (31) :10514-10521

[8] Enantioselective and Enantiospecific Transition-Metal-Catalyzed Cross-Coupling Reactions of Organometallic Reagents To Construct C-C Bonds [J].

Cherney, Alan H. ;

Kadunce, Nathaniel T. ;

Reisman, Sarah E. .

CHEMICAL REVIEWS, 2015, 115 (17) :9587-9652

[9] Site-Selective Nitration of Aryl Germanes at Room Temperature [J].

Dahiya, Amit ;

Gevondian, Avetik G. ;

Selmani, Aymane ;

Schoenebeck, Franziska .

ORGANIC LETTERS, 2023, 25 (39) :7209-7213

[10] Orthogonal Olefination with Organogermanes [J].

Dahiya, Amit ;

Schoetz, Markus D. ;

Schoenebeck, Franziska .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2023, 62 (43)

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