stereochemistry Stereochemistry, a subdiscipline of chemistry, studies the spatial arrangement of atoms that form the structure of molecules and their manipulation. The study of stereochemistry focuses on the relationships between stereoisomers, which are defined ...

, torquoselectivity is a special kind of

stereoselectivity In chemistry, stereoselectivity is the property of a chemical reaction in which a single reactant forms an unequal mixture of stereoisomers during a non- stereospecific creation of a new stereocenter or during a non-stereospecific transformation ...

observed in

electrocyclic reaction In organic chemistry, an electrocyclic reaction is a type of pericyclic reaction, pericyclic, rearrangement reaction, rearrangement reaction where the net result is one pi bond being converted into one sigma bond or vice versa. These reactions are ...

s, defined as "the preference for inward or outward rotation of

substituents In organic chemistry, a substituent is one or a group of atoms that replaces (one or more) atoms, thereby becoming a moiety (chemistry), moiety in the resultant (new) molecule. The suffix ''-yl'' is used when naming organic compounds that conta ...

in conrotatory or disrotatory electrocyclic reactions." Torquoselectivity is not to be confused with the normal

diastereoselectivity In stereochemistry, diastereomers (sometimes called diastereoisomers) are a type of stereoisomer. Diastereomers are defined as non-mirror image, non-identical stereoisomers. Hence, they occur when two or more stereoisomers of a compound have d ...

seen in

pericyclic reaction In organic chemistry, a pericyclic reaction is the type of organic reaction wherein the transition state of the molecule has a cyclic geometry, the reaction progresses in a concerted fashion, and the bond orbitals involved in the reaction overl ...

s, as it represents a further level of selectivity beyond the Woodward-Hoffman rules. The name derives from the idea that the substituents in an electrocyclization appear to rotate over the course of the reaction, and thus selection of a single product is equivalent to selection of one direction of rotation (i.e. the direction of

torque In physics and mechanics, torque is the rotational analogue of linear force. It is also referred to as the moment of force (also abbreviated to moment). The symbol for torque is typically \boldsymbol\tau, the lowercase Greek letter ''tau''. Wh ...

on the substituents). The concept was originally developed by American chemist Kendall N. Houk. For

ring closing reaction A cyclic compound (or ring compound) is a term for a compound in the field of chemistry in which one or more series of atoms in the compound is connected to form a ring. Rings may vary in size from three to many atoms, and include examples where ...

s, it is an example of

enantioselectivity In chemistry, stereoselectivity is the property of a chemical reaction in which a single reactant forms an unequal mixture of stereoisomers during a non- stereospecific creation of a new stereocenter or during a non-stereospecific transformation o ...

, wherein a single

enantiomer In chemistry, an enantiomer (Help:IPA/English, /ɪˈnænti.əmər, ɛ-, -oʊ-/ Help:Pronunciation respelling key, ''ih-NAN-tee-ə-mər''), also known as an optical isomer, antipode, or optical antipode, is one of a pair of molecular entities whi ...

of a cyclization product is formed from the selective ring closure of the starting material. In a typical electrocyclic ring closing, selection for either conrotatory or disrotatory reactions modes still produces two enantiomers. Torquoselectivity is a discrimination ''between'' these possible enantiomers that requires asymmetric induction. Torquo

Torquoselectivity is also used to describe selective electrocyclic ring openings, in which different directions of rotation produce distinct

structural isomers In chemistry, a structural isomer (or constitutional isomer in the IUPAC nomenclature) of a chemical compound, compound is a compound that contains the same number and type of atoms, but with a different connectivity (i.e. arrangement of chemica ...

. In these cases,

steric strain Van der Waals strain is strain resulting from Van der Waals repulsion when two substituents in a molecule approach each other with a distance less than the sum of their Van der Waals radii. Van der Waals strain is also called Van der Waals repul ...

is often the driving force for the selectivity. Studies have shown that the selectivity can also be changed by the presence of electron donating and

electron withdrawing group The electron (, or in nuclear reactions) is a subatomic particle with a negative one elementary electric charge. It is a fundamental particle that comprises the ordinary matter that makes up the universe, along with up and down quarks. E ...

Other mechanisms by which torquoselectivity can operate include

chiral Chirality () is a property of asymmetry important in several branches of science. The word ''chirality'' is derived from the Greek language, Greek (''kheir''), "hand", a familiar chiral object. An object or a system is ''chiral'' if it is dist ...

Lewis acid A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any ...

catalyst Catalysis () is the increase in rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quick ...

s, induction via neighboring

stereocenter In stereochemistry, a stereocenter of a molecule is an atom (center), axis or plane that is the focus of stereoisomerism; that is, when having at least three different groups bound to the stereocenter, interchanging any two different groups cr ...

s (in which case the torquoselectivity is a case of

), and axial-to-tetrahedral chirality transfer. An example of the latter case is shown below for the torquoselective

Nazarov cyclization reaction The Nazarov cyclization reaction (often referred to as simply the Nazarov cyclization) is a chemical reaction used in organic chemistry for the synthesis of cyclopentenones. The reaction is typically divided into ''classical'' and ''modern'' vari ...

of a chiral allenyl vinyl ketone. Axialtotetrahedral transfer

References

{{Reflist Stereochemistry