Formal total synthesis of fostriecin by 1,4-asymmetric induction with an alkyne-cobalt complex

Chemistry : a European Journal
Yujiro HayashiMitsuru Shoji

Abstract

The synthesis of a protected dephosphofostriecin, and thereby a formal synthesis of fostriecin, has been accomplished. The synthetic challenges were the construction of four stereogenic centers and the conformationally labile cis-cis-trans-triene moiety. Previous total syntheses have employed at least two asymmetric reactions that required the use of an external chiral auxiliary. Although remote stereoinduction in a 1,4-relationship is considered difficult, we have developed a notable 1,4-asymmetric induction that utilizes an alkyne-cobalt complex for the control of C5 stereochemistry by the C8 stereogenic center. The stereochemistry at C11 was established by 1,3-asymmetric induction with a higher-order alkynyl-zinc reagent. Thus, only one asymmetric reaction requiring an external chiral auxiliary was employed in this route. The labile cis-cis-trans-triene unit was constructed at a late stage of the synthesis by diastereoselective coupling of a dienyne and an aldehyde unit, followed by reduction.

References

Aug 1, 1986·European Journal of Cancer & Clinical Oncology·W ScheithauerE F Elslager
Dec 1, 1983·The Journal of Antibiotics·S S StampwalaJ C French
Jun 1, 1997·Anti-cancer Drugs·R S de JongN H Mulder
Feb 15, 2001·Accounts of Chemical Research·T M Trnka, R H Grubbs
Jul 7, 2001·Organic Letters·J CossyS BouzBouz
Jul 18, 2001·Journal of the American Chemical Society·D L BogerW Zhong
Mar 8, 2002·Journal of Medicinal Chemistry·Adam McCluskeyJennette A Sakoff
Mar 15, 2002·Organic Letters·Y Krishna Reddy, J R Falck
Jul 18, 2002·Chemical Communications : Chem Comm·Kazuyuki MiyashitaTakeshi Imanishi
Oct 9, 2002·Current Medicinal Chemistry·D S LewyD L Boger
Dec 20, 2002·Organic Letters·Yong-Gang Wang, Yuichi Kobayashi
Jan 23, 2003·Chemical Communications : Chem Comm·Tomoyuki EsumiSusumi Hatakeyama
Feb 6, 2003·Journal of the American Chemical Society·Keiji TaninoIsao Kuwajima
Feb 28, 2003·Organic Letters·Kunihiko FujiiMasakatsu Shibasaki
Apr 3, 2003·Journal of the American Chemical Society·Kousei ShimadaTohru Fukuyama
May 2, 2003·Angewandte Chemie·Susan E Gibson, Andrea Stevenazzi
Jul 3, 2003·Journal of the American Chemical Society·Kazuyuki MiyashitaTakeshi Imanishi
Jan 23, 2004·Chemical Society Reviews·Jaime Blanco-UrgoitiJavier Pérez-Castells
Mar 18, 2005·Journal of the American Chemical Society·Barry M TrostBrock T Shireman
Dec 1, 2005·Journal of the American Chemical Society·Keisuke MakiMasakatsu Shibasaki
Mar 19, 2009·Angewandte Chemie·Akinari Hamajima, Minoru Isobe

❮ Previous
Next ❯

Citations

May 12, 2011·Chemical Communications : Chem Comm·Yanping WangGeorge A O'Doherty
Jun 23, 2021·Journal of Medicinal Chemistry·Qiuyue ZhangLei Wang
May 18, 2012·Journal of the American Chemical Society·Crispin LichtenbergJun Okuda
Nov 19, 2019·ACS Omega·Mariam A MehdiJames R Green
Dec 29, 2016·Chemical Reviews·Barry M TrostCheyenne S Brindle
Oct 5, 2019·Organic Letters·Dong GaoGeorge A O'Doherty
Jul 20, 2018·The Journal of Organic Chemistry·Yuya YamasakiTakuya Kochi

❮ 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.