NDLI: Stereodivergent, Diels–Alder-initiated organocascades employing α,β-unsaturated acylammonium salts: scope, mechanism, and application

Content Provider	Royal Society of Chemistry (RSC)
Author	Abbasov, Mikail E. Romo, Daniel Tantillo, Dean J. Hudson, Brandi M.
Copyright Year	2017
Abstract	Chiral α,β-unsaturated acylammonium salts are novel dienophiles enabling enantioselective Diels–Alder-lactonization (DAL) organocascades leading to cis- and trans-fused, bicyclic γ- and δ-lactones from readily prepared dienes, commodity acid chlorides, and a chiral isothiourea organocatalyst under mild conditions. We describe extensions of stereodivergent DAL organocascades to other racemic dienes bearing pendant secondary and tertiary alcohols, and application to a formal synthesis of (+)-dihydrocompactin is described. A combined experimental and computational investigation of unsaturated acylammonium salt formation and the entire DAL organocascade pathway provide a rationalization of the effect of Brønsted base additives and enabled a controllable, diastereodivergent DAL process leading to a full complement of possible stereoisomeric products. Evaluation of free energy and enthalpy barriers in conjunction with experimentally observed temperature effects revealed that the DAL is a rare case of an entropy-controlled diastereoselective process. NMR analysis of diene alcohol–Brønsted base interactions and computational studies provide a plausible explanation of observed stabilization of exo transition-state structures through hydrogen-bonding effects.
Starting Page	1511
Ending Page	1524
Page Count	14
File Format	HTM / HTML PDF
ISSN	20416520
Volume Number	8
Issue Number	2
Journal	Chemical Science
DOI	10.1039/c6sc04273b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Subscribed
Subject Keyword	Racemic mixture Carboxylic acid Enantiomer Enthalpy Nuclear magnetic resonance Organocatalysis Total synthesis Nsted
Content Type	Text
Resource Type	Article
Subject	Chemistry

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