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在钛亚胺模板上对甲基取代的炔烃进行选择性炔丙基C(sp)-H活化及[2 + 2]环加成反应。

Selective propargylic C(sp)-H activation of methyl-substituted alkynes [2 + 2] cycloaddition at a titanium imido template.

作者信息

Fischer Malte, Manßen Manfred, Schmidtmann Marc, Klüner Thorsten, Beckhaus Rüdiger

机构信息

Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford South Parks Road Oxford OX1 3QR UK

Institut für Chemie, Fakultät für Mathematik und Naturwissenschaften, Carl von Ossietzky Universität Oldenburg Postfach 2503 D-26111 Oldenburg Germany

出版信息

Chem Sci. 2021 Sep 28;12(41):13711-13718. doi: 10.1039/d1sc04334j. eCollection 2021 Oct 27.

DOI:10.1039/d1sc04334j
PMID:34760155
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8549805/
Abstract

The reaction of the titanium imido complex with 2-butyne leads to the formation of the titanium azadiene complex at ambient temperature instead of yielding the archetypical [2 + 2] cycloaddition product (titanaazacyclobutene) which is usually obtained by combining titanium imido complexes and internal alkynes. The formation of is presumably caused by an initial propargylic C(sp)-H activation step and quantum chemical calculations suggest that the outcome of this unexpected reactivity is thermodynamically favored. The previously reported titanaazacyclobutene (which is obtained by reacting with 1-phenyl-1-propyne) undergoes a rearrangement reaction at elevated temperature to give the corresponding five-membered titanium azadiene complex .

摘要

亚氨基钛配合物与2-丁炔的反应在室温下生成了氮杂二烯钛配合物，而不是生成典型的[2 + 2]环加成产物（氮杂环丁烯钛），后者通常是通过亚氨基钛配合物与内炔烃反应得到的。的形成可能是由最初的炔丙基C(sp)-H活化步骤引起的，量子化学计算表明这种意外反应的结果在热力学上是有利的。先前报道的氮杂环丁烯钛（通过与1-苯基-1-丙炔反应得到）在高温下发生重排反应，生成相应的五元氮杂二烯钛配合物。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e14/8549805/0080c5a91ad3/d1sc04334j-s6.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e14/8549805/0e71c764b4d1/d1sc04334j-s4.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e14/8549805/4d7a68d35e5a/d1sc04334j-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e14/8549805/0080c5a91ad3/d1sc04334j-s6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e14/8549805/2d7bf5972fa0/d1sc04334j-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e14/8549805/12c67fb3d8f0/d1sc04334j-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e14/8549805/cef7a16d7c73/d1sc04334j-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e14/8549805/e18849807600/d1sc04334j-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e14/8549805/0e71c764b4d1/d1sc04334j-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e14/8549805/19dac5925bae/d1sc04334j-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e14/8549805/c0cd3ea04c8d/d1sc04334j-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e14/8549805/4d7a68d35e5a/d1sc04334j-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/8e14/8549805/0080c5a91ad3/d1sc04334j-s6.jpg

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