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通过钯（II）/双亚砜/布朗斯特酸共催化的烯丙基C-H氧化反应将N-叔丁氧羰基胺转化为恶唑烷酮。

N-Boc amines to oxazolidinones via Pd(II)/bis-sulfoxide/Brønsted acid co-catalyzed allylic C-H oxidation.

作者信息

Osberger Thomas J, White M Christina

机构信息

Roger Adams Laboratory, University of Illinois Urbana-Champaign , Champaign, Illinois 61801, United States.

出版信息

J Am Chem Soc. 2014 Aug 6;136(31):11176-81. doi: 10.1021/ja506036q. Epub 2014 Jul 24.

DOI:10.1021/ja506036q
PMID:24999765
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC4132963/
Abstract

A Pd(II)/bis-sulfoxide/Brønsted acid catalyzed allylic C-H oxidation reaction for the synthesis of oxazolidinones from simple N-Boc amines is reported. A range of oxazolidinones are furnished in good yields (avg 63%) and excellent diastereoselectivities (avg 15:1) to furnish products regioisomeric from those previously obtained using allylic C-H amination reactions. Mechanistic studies suggest the role of the phosphoric acid is to furnish a Pd(II)bis-sulfoxide phosphate catalyst that promotes allylic C-H cleavage and π-allylPd functionalization with a weak, aprotic oxygen nucleophile and to assist in catalyst regeneration.

摘要

报道了一种钯（II）/双亚砜/布朗斯特酸催化的烯丙基C-H氧化反应，用于从简单的N-叔丁氧羰基胺合成恶唑烷酮。一系列恶唑烷酮以良好的产率（平均63%）和优异的非对映选择性（平均15:1）得到，产物的区域异构体与之前使用烯丙基C-H胺化反应得到的不同。机理研究表明，磷酸的作用是提供一种钯（II）双亚砜磷酸盐催化剂，该催化剂促进烯丙基C-H裂解和与弱的非质子氧亲核试剂进行π-烯丙基钯官能化，并协助催化剂再生。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0c30/4132963/2e48c89e130a/ja-2014-06036q_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0c30/4132963/1625d397be41/ja-2014-06036q_0011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0c30/4132963/472864058791/ja-2014-06036q_0012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0c30/4132963/8a0c00d91af0/ja-2014-06036q_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0c30/4132963/d68cfd20d421/ja-2014-06036q_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0c30/4132963/fce7c95b9ed4/ja-2014-06036q_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0c30/4132963/2e48c89e130a/ja-2014-06036q_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0c30/4132963/1625d397be41/ja-2014-06036q_0011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0c30/4132963/472864058791/ja-2014-06036q_0012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0c30/4132963/8a0c00d91af0/ja-2014-06036q_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0c30/4132963/d68cfd20d421/ja-2014-06036q_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0c30/4132963/fce7c95b9ed4/ja-2014-06036q_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0c30/4132963/2e48c89e130a/ja-2014-06036q_0004.jpg

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