Iterative, Programmable, and Controllable De Novo Synthesis of Fully Heteroleptic All-Carbon Substituted Silanes from Four Different Organometallic Reagents DOI Creative Commons
Xin Xu, Xinyu Zhang, Chao Wang

et al.

Published: Aug. 20, 2024

All-carbon substituted silanes are a class of unnatural yet important compounds. To access them from SiCl4 or Si(OR)4 and organometallic reagents is intuitively the most straightforward de novo approach, which unfortunately only applicable to homoleptic but not heteroleptic ones. Thus, alternative silyl precursors techniques enable controllable substitutions at silicon highly desirable. Herein, we targeted structurally complicated synthetically challenging fully all-carbon developed Ph3SiCl Ph2Si(OMe)2 as synthetic equivalent for synthesis them. Mono-selective dephenylative etherifications triphenyl-substituted well diphenyl-substituted ones were key success. Within 5-7 steps, four different carbon units could be ligated one center in controllable, programmable, iterative fashion. Meanwhile, unique reactivities hexafluoroisopropoxysilanes with hemicrown ether auxiliaries substitution reactions disclosed.

Language: Английский

Single-Atom Ligation of Four Different Alcohols at One Silicon Center: Methodology Development and Proof of Concept DOI Creative Commons
Chao Wang, Xin Xu, Xinyu Zhang

et al.

Published: April 9, 2024

Click chemistry continues to impact the and biology community, with most well-known being CuAAC click chemistry. Topologically, only ligated two fragments in a two-dimensional manner. While SuFEx PFEx could ligate three-dimensionally, maximally three (amine/alcohol) be clicked together for now. Herein, we report three-dimensional single-atom ligation of four different (alcohols) at one silicon center using triphenylchlorosilane as hub an iterative, controllable, programmable fashion. To fulfill mission, established new silicon-phenyl exchange reaction alcohols. A broad spectrum alcohols various types phenylchlorosilanes hubs, affording library mixed-dialkoxysilanes, trialkoxysilanes, tetraalkoxysilanes. Notably, fully heteroleptic tetraalkoxysilanes were barely known literature extremely difficult access selective fashion from retrosynthetic viewpoint. Our protocol thus provided robust solution materials such nature. highlight application potential, biologically relevant alcohols, representing functions, successfully Si(IV) tetraalkoxysilane. More importantly, released recovered via silicon-alkoxy stable yet cleavable Si-O bonds.

Language: Английский

Citations

2
Iterative, Programmable, and Controllable De Novo Synthesis of Fully Heteroleptic All-Carbon Substituted Silanes from Four Different Organometallic Reagents DOI Creative Commons
Xin Xu, Xinyu Zhang, Chao Wang

et al.

Published: Aug. 20, 2024

All-carbon substituted silanes are a class of unnatural yet important compounds. To access them from SiCl4 or Si(OR)4 and organometallic reagents is intuitively the most straightforward de novo approach, which unfortunately only applicable to homoleptic but not heteroleptic ones. Thus, alternative silyl precursors techniques enable controllable substitutions at silicon highly desirable. Herein, we targeted structurally complicated synthetically challenging fully all-carbon developed Ph3SiCl Ph2Si(OMe)2 as synthetic equivalent for synthesis them. Mono-selective dephenylative etherifications triphenyl-substituted well diphenyl-substituted ones were key success. Within 5-7 steps, four different carbon units could be ligated one center in controllable, programmable, iterative fashion. Meanwhile, unique reactivities hexafluoroisopropoxysilanes with hemicrown ether auxiliaries substitution reactions disclosed.

Language: Английский

Citations

1