Steric Strain

Author(s):  
I. David Brown
Keyword(s):  
Author(s):  
Victor J. Baker ◽  
Alan R. Katritzky ◽  
Jean-Pierre Majoral ◽  
Stephen F. Nelsen ◽  
Patrick J. Hintz

2011 ◽  
Vol 64 (5) ◽  
pp. 583 ◽  
Author(s):  
Biswajit Saha ◽  
S. M. Wahidur Rahaman ◽  
Arup Sinha ◽  
Jitendra K. Bera

Reaction of cis-[Rh2(CH3COO)2(CH3CN)6](BF4)2 with two equivalents of 2-mesityl-1,8-naphthyridine (Mes-NP) affords trans-[Rh2(CH3COO)2(Mes-NP)2](BF4)2 (1). X-ray structure reveals weak Rh–C(ipso) interaction, and a short Rh–Rh distance. The same ligand, in contrast, oxidatively cleaves the Ru–Ru bond in cis-[Ru2(CO)4(CH3CN)6](BF4)2 and results in trans-[Ru(Mes-NP)2(CH3CN)2](BF4)2 (2). Both compounds adopt trans geometry to relieve the steric strain. Compound 2 exhibits moderate activity for the alcohol oxidation and aldehyde olefination reactions.


1983 ◽  
Vol 20 (2) ◽  
pp. 139-146 ◽  
Author(s):  
Wayne Levin ◽  
Alexander W. Wood ◽  
Richard L. Chang ◽  
Melvin S. Newman ◽  
Dhiren R. Thakker ◽  
...  

1979 ◽  
Vol 57 (21) ◽  
pp. 2823-2826 ◽  
Author(s):  
Jean-Pierre Aycard ◽  
Ronald Lafrance ◽  
Bernard Boyer

The cyano group effect on diastereoselectivity is studied through the reduction of cis and trans 3-R 4-cyano cyclohexanones with NaBH4; the diastereoselectivity (zero for R = H) is 74 and 62% respectively (R = CH3) and 74 and 50% (R = (CH3)3C), the more stable isomer being always the major one. These stereoselectivities are rationalized from the experimental values of free enthalpy between conformers and from the diastereoselectivities of the 3-t-butyl (and 4-t-butyl) cyclohexanones, cis 3,5-dimethyl and 3,3,5-trimethyl cyclohexanones, without taking account of a cyano group specific effect. The decrease in diastereoselectivity for R = (CH3)3C (trans isomer) is associated with deformation induced by steric strain between the substituents.


2001 ◽  
Vol 56 (4-5) ◽  
pp. 354-358
Author(s):  
Teresa Borowiak ◽  
Irena Wolska ◽  
Herbert Mayr ◽  
Janusz Baran

Abstract The X-ray crystallographic structure of the title compound, a product of a 1,3-dipolar cy­ cloaddition reaction of benzonitrile oxide to 3,3,4,4,5,5-hexamethyl-1,2-bis(methylene)cyclopentane, has been determined. Colourless plates crystallize in the orthorhombic space group Pbca with cell dimensions a = 13.698(2), b = 11.836(2), c = 29.157(4) Å, V= 4727.2(1.2)Å3, Z = 8, 3736 reflections, final R(F) = 0.063 and wR(F2) = 0.166. The crystals are racemic, the molecules of opposite chirality form centrosymmetric dimers via intermolecular hydro­ gen bonds O-H···N between their oxime groups. The molecules are highly strained and the geometrical consequences of the steric strain are discussed.


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