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A Computational Determination of the Origins of Diastereoselective Alkylations of a Cysteinesulfenate Anion
Author(s) -
Schwan Adrian L.
Publication year - 2019
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201801053
Subject(s) - chemistry , stereoselectivity , alkylation , lithium (medication) , density functional theory , hydrogen bond , functional group , sulfenic acid , counterion , medicinal chemistry , ion , steric effects , hydrogen , computational chemistry , stereochemistry , organic chemistry , molecule , catalysis , enzyme , medicine , polymer , cysteine , endocrinology
Sulfenic acid anions (RSO – ) represent an untapped functional group for the formation of sulfoxides and other organic compounds. Their stereoselective alkylation is an important component of this chemistry, but factors governing reaction outcomes are not fully understood. The current study uses Density Functional Theory methods to break down the influencing roles of substituents attached to 2‐aminoethanesulfenate. The lithium counterion can be coordinated to pendant ester or carbamate carbonyl groups, whereas the sulfenate oxygen readily participates in hydrogen bonding with proximal hydrogen atoms of the (protected) amino group. A Moc‐protected, ester substituted, 2‐aminoethanesulfenate adopts both lithium coordination and hydrogen bonding in the lowest energy form and demonstrates stereoselective methylation and benzylation consistent with experiments from the literature.