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Henry Rzepa's Blog

Henry Rzepa's Blog
Chemistry with a twist
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ChiropticsCiencias QuímicasInglés
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Nature has produced most natural molecules as chiral objects, which means the molecule can come in two enantiomeric forms, each being the mirror image of the other. When a natural product is synthesised in a laboratory, a chiral synthesis means just one form is made, and then is compared with the natural product to see if it matches.

Ciencias QuímicasInglés
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The list of molecules of the year is out now at C&E News (but you have to have an account to view the list, unlike previous years). These three caught my eye: Electron in a cube: Synthesis and characterization of perfluorocubane as an electron acceptor ,[cite]10.1126/science.abq0516[/cite]. I have already written about this system and will not discuss it further, except to note this one topped the poll!

Reaction MechanismCiencias QuímicasInglés
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The term bispericyclic reaction was famously coined by Caramella et a l in 2002[cite]10.1021/ja016622h[/cite] to describe the unusual features of the apparently innocuous dimerisation of cyclopentadiene. It shows features of two paths for different pericyclic reactions, comprising a 2+4 cycloaddition in the early stages, but evolving into a (degenerate) pair of [3,3] sigmatropic reactions in the latter stages.

Interesting ChemistryCiencias QuímicasInglés
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Four-coordinate carbon normally adopts a tetrahedral shape, where the four angles at the carbon are all 109.47°. But how large can that angle get, and can it even get to be 180°? A search of the CSD (crystal structure database) reveals a spiropentane as having the largest such angle, VAJHAP with 164°[cite]10.1021/ja00186a058[/cite] Because crystal structures might have artefacts such as disorder etc, it is always good to check this with a