Computational and experimental investigation on the BCl3 promoted intramolecular amination of alkenes and alkynes

Organic & Biomolecular Chemistry
Wei LiuYong Liang

Abstract

The BX3 promoted transition-metal-free borylative cyclizations have recently attracted increasing attention. In 2015, the Li group reported a BCl3 mediated aminoboration of unfunctionalized olefins. In their originally proposed reaction pathways, the overall reaction barrier was calculated to be about 35 kcal mol-1, which is too high to be reasonable for a reaction that smoothly occurs at room temperature. Through DFT calculations, we have reinvestigated the mechanism of this reaction and found a much more favorable reaction pathway with a computed activation free energy of about 20 kcal mol-1. Based on this new mechanism, we then calculated the energy profiles for the BCl3 promoted corresponding aminoboration of alkynes. According to the computational prediction, this transformation could easily take place at room temperature. Later experiments show that the aminoboration product is indeed generated, but the major product of this reaction is the hydroamination product. Through further calculations, we found that an unexpected protodeboronation is quite favored both kinetically and thermodynamically at the post-aminoborylation stage. Finally, we optimized the conditions for the newly discovered metal-free hydroamination reactio...Continue Reading

References

Apr 1, 2003·Journal of Computational Chemistry·Maurizio CossiVincenzo Barone
May 7, 2005·The Journal of Organic Chemistry·Giorgio AbbiatiSimona Zanzola
Mar 14, 2007·Journal of the American Chemical Society·Jennifer M SchomakerBabak Borhan
May 26, 2007·Angewandte Chemie·Jenny S J McCahillDouglas W Stephan
Jun 15, 2007·Angewandte Chemie·Kelvin L BillingsleyStephen L Buchwald
Jul 31, 2007·Chemical Society Reviews·René Severin, Sven Doye
Jan 12, 2008·Accounts of Chemical Research·Yan Zhao, Donald G Truhlar
Jan 19, 2008·Angewandte Chemie·André M BeaucheminSerge I Gorelsky
Aug 30, 2008·Chemical Reviews·Thomas E MüllerMizuki Tada
Dec 5, 2008·Journal of the American Chemical Society·Joseph MoranAndré M Beauchemin
May 8, 2009·Dalton Transactions : an International Journal of Inorganic Chemistry·Douglas W Stephan
Dec 24, 2009·Chemical Reviews·Ibraheem A I MkhalidJohn F Hartwig
Jun 15, 2010·Chemical Reviews·Casey R WadeFrançois P Gabbaï
Nov 26, 2010·The Journal of Organic Chemistry·Naoki IshidaMasahiro Murakami
Nov 26, 2010·Journal of the American Chemical Society·Gary A MolanderSpencer D Dreher
Feb 24, 2011·Angewandte Chemie·Alessandro Del GrossoMichael J Ingleson
Mar 5, 2011·Organic Letters·Akhilesh Kumar VermaVed Prakash Singh
Dec 1, 2011·Organic Letters·Masahito YamagishiHirokazu Urabe
Jan 14, 2012·Angewandte Chemie·Juri MöbusGerhard Erker
Mar 1, 2012·Organic Letters·René LiedtkeGerhard Erker
Jun 30, 2012·Organic Letters·Aman KulshresthaBabak Borhan
Aug 8, 2013·Chemistry : a European Journal·Rebecca L MelenDouglas W Stephan
Oct 12, 2013·Angewandte Chemie·Tayseer Mahdi, Douglas W Stephan
Oct 18, 2013·Dalton Transactions : an International Journal of Inorganic Chemistry·Juri MöbusGerhard Erker
Nov 13, 2013·The Journal of Organic Chemistry·Akhilesh K VermaKeykavous Parang
Dec 21, 2013·Journal of the American Chemical Society·Max M HansmannDouglas W Stephan
Feb 21, 2014·Chemical Society Reviews·A RosJ M Lassaletta
May 13, 2014·Chemical Communications : Chem Comm·Max M HansmannDouglas W Stephan
Jun 26, 2014·Angewandte Chemie·Alexandre HentzRobert H Dodd
Dec 11, 2014·Accounts of Chemical Research·Mark S Taylor
Mar 17, 2015·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Alexander BährRebecca L Melen
Jun 26, 2015·Chemistry : a European Journal·Tayseer Mahdi, Douglas W Stephan
Aug 4, 2015·Angewandte Chemie·Andrew J WarnerMichael J Ingleson
Sep 4, 2015·Angewandte Chemie·Chun-Hua YangYue-Ming Li
Nov 12, 2015·Chemistry : a European Journal·Christoph RosoriusGerhard Erker

❮ Previous
Next ❯

Citations

Mar 27, 2021·Inorganic Chemistry·Shengwen YangVincent Gandon
Jun 20, 2020·Organic Letters·Chun-Hua YangYue-Ming Li
Sep 28, 2021·Organic & Biomolecular Chemistry·Ryukichi Takagi, Duyen Thi Duong
Sep 10, 2021·Chemistry : a European Journal·Dmitriy M VolochnyukOleksandr O Grygorenko

❮ Previous
Next ❯

Methods Mentioned

BETA
hydroamination

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.