Catalytic, efficient, and syn-selective construction of deoxypolypropionates and other chiral compounds via Zr-catalyzed asymmetric carboalumination of allyl alcohol

Journal of the American Chemical Society
Bo LiangEi-ichi Negishi

Abstract

An efficient, syn-selective, all catalytic asymmetric protocol for the synthesis of alpha,omega-diheterofunctional deoxypolypropionates via Zr-catalyzed asymmetric carboalumination (ZACA reaction) was developed. The success of the method critically hinges on the one-pot conversion of unprotected allyl alcohol into TBS-protected (R)- or (S)-3-iodo-2-methyl-1-propanol (1) of 91% enantiomeric purity in 82% yield via (i) Zr-catalyzed asymmetric methylalumination, (ii) iodination, and (iii) protection with TBSCl. After zincation of 1, its Pd-catalyzed cross-coupling with various organic halides can give various organic derivatives, including 3 and 4, which can serve as key intermediates for efficient and selective syntheses of deoxypolypropionates, such as doliculide and 2,4,6,8-tetramethyldecanoic acid, and other chiral compounds, such as callystatin A. Selective monocarboalumination of 1,4-pentadiene (5 equiv) gave, after oxidation, the expected product 5, but it was 0% ee. A plausible mechanism for racemization has been proposed and experimentally supported.

References

Feb 17, 2001·Organic Letters·A K Ghosh, C Liu
Oct 30, 2001·The Journal of Organic Chemistry·M A CalterJ A Struss
Nov 6, 2003·Journal of the American Chemical Society·Xingzhong ZengEi-ichi Negishi
Apr 10, 2004·Proceedings of the National Academy of Sciences of the United States of America·Ei-Ichi NegishiTibor Novak
Jun 24, 2004·Proceedings of the National Academy of Sciences of the United States of America·Stephen HanessianSimon Giroux
Aug 28, 2004·Organic Letters·Neil F Langille, James S Panek

❮ Previous
Next ❯

Citations

May 8, 2009·Chemical Society Reviews·Thomas JerphagnonBen L Feringa
May 8, 2010·Chemical Communications : Chem Comm·Bjorn ter HorstAdriaan J Minnaard
Mar 8, 2014·Molecular Diversity·Majid M HeraviNiousha Nazari
Feb 26, 2016·Proceedings of the National Academy of Sciences of the United States of America·Yusuke OtaKyoko Nozaki
Mar 8, 2018·Chemistry : a European Journal·Kodai KatoMasahiro Miura
Nov 3, 2016·Angewandte Chemie·Barry M Trost, Michael C Ryan
Apr 21, 2007·Angewandte Chemie·Robert E MulveyYoshinori Kondo
May 10, 2007·Angewandte Chemie·J Russell FalckAkella Radha
Nov 24, 2007·Chemistry : a European Journal·Shinji NakamuraMasanobu Uchiyama
Jan 15, 2009·Angewandte Chemie·Stefan H Wunderlich, Paul Knochel
Jan 26, 2007·Chemical Communications : Chem Comm·Bjorn ter HorstAdriaan J Minnaard
Jan 15, 2016·Angewandte Chemie·John R Coombs, James P Morken
Nov 12, 2013·Organic & Biomolecular Chemistry·Norazah BasarEric J Thomas
Jun 20, 2015·Angewandte Chemie·Shiqing XuEi-ichi Negishi
Nov 8, 2008·Journal of the American Chemical Society·Hiroshi NakaAndrew E H Wheatley
Aug 2, 2012·The Journal of Organic Chemistry·Cyril CookEmmanuel Roulland
Dec 24, 2014·The Journal of Organic Chemistry·Shekar Mekala, Roger C Hahn
Mar 1, 2007·Journal of the American Chemical Society·Paul R Blakemore, Matthew S Burge

❮ Previous
Next ❯

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.