@article{89bda487b2be422ca37f359e9192fab3,
title = "Rapid Entry into Biologically Relevant α,α-Difluoroalkylphosphonates Bearing Allyl Protection-Deblocking under Ru(II)/(IV)-Catalysis",
abstract = "A convenient synthetic route to α,α-difluoroalkylphosphonates is described. Structurally diverse aldehydes are condensed with LiF2CP(O)(OCH2CH═CH2)2. The resultant alcohols are captured as the pentafluorophenyl thionocarbonates and efficiently deoxygenated with HSnBu3, BEt3, and O2, and then smoothly deblocked with CpRu(IV)(π-allyl)quinoline-2-carboxylate (1-2 mol %) in methanol as an allyl cation scavenger. These mild deprotection conditions provide access to free α,α-difluoroalkylphosphonates in nearly quantitative yield. This methodology is used to rapidly construct new bis-α,α-difluoroalkyl phosphonate inhibitors of PTPIB (protein phosphotyrosine phosphatase-1B).",
author = "Kaushik Panigrahi and Xiang Fei and Masato Kitamura and Berkowitz, {David B.}",
note = "Funding Information: This work was supported in part by NSF CHE-1500076 and CHE-1800574. These studies were initiated by a JSPS Fellowship to D.B.B. that brought D.B.B. and M.K. together and were facilitated by the IR/D program for D.B.B.{\textquoteright}s appointment at the NSF. The authors thank Martin Osinde and Ranjeet Dhokale (both of the University of Nebraska) for assistance with modeling and data analysis, respectively; the NIH (SIG-1-510-RR-06307) and NSF (CHE-0091975 and MRI-0079750) for NMR instrumentation; and the NIH (RR016544) for facilities. Funding Information: This work was supported in part by NSF CHE-1500076 and CHE-1800574. These studies were initiated by a JSPS Fellowship to D.B.B. that brought D.B.B. and M.K. together and were facilitated by the IR/D program for D.B.B.'s appointment at the NSF. The authors thank Martin Osinde and Ranjeet Dhokale (both of the University of Nebraska) for assistance with modeling and data analysis, respectively; the NIH (SIG-1-510-RR-06307) and NSF (CHE-0091975 and MRI-0079750) for NMR instrumentation; and the NIH (RR016544) for facilities. Publisher Copyright: Copyright {\textcopyright} 2019 American Chemical Society.",
year = "2019",
month = dec,
day = "20",
doi = "10.1021/acs.orglett.9b03707",
language = "English (US)",
volume = "21",
pages = "9846--9851",
journal = "Organic Letters",
issn = "1523-7060",
publisher = "American Chemical Society",
number = "24",
}