Review

. 2018 Sep 11;23(9):2317.

doi: 10.3390/molecules23092317.

Chiral Diol-Based Organocatalysts in Enantioselective Reactions

Truong N Nguyen¹, Po-An Chen², Krit Setthakarn³, Jeremy A May⁴

Affiliations

¹ Department of Chemistry, University of Houston, 3585 Cullen Boulevard, Fleming Building Room 112, Houston, TX 77204-5003, USA. tnnguyen61@uh.edu.
² Department of Chemistry, University of Houston, 3585 Cullen Boulevard, Fleming Building Room 112, Houston, TX 77204-5003, USA. pchen25@central.uh.edu.
³ Department of Chemistry, Faculty of Science, Silpakorn University, Nakhon Pathom 73000, Thailand. krit_set@silpakorn.edu.
⁴ Department of Chemistry, University of Houston, 3585 Cullen Boulevard, Fleming Building Room 112, Houston, TX 77204-5003, USA. jmay@uh.edu.

PMID: 30208621
PMCID: PMC6225256
DOI: 10.3390/molecules23092317

Review

Chiral Diol-Based Organocatalysts in Enantioselective Reactions

Truong N Nguyen et al. Molecules. 2018.

. 2018 Sep 11;23(9):2317.

doi: 10.3390/molecules23092317.

Authors

Truong N Nguyen¹, Po-An Chen², Krit Setthakarn³, Jeremy A May⁴

Affiliations

¹ Department of Chemistry, University of Houston, 3585 Cullen Boulevard, Fleming Building Room 112, Houston, TX 77204-5003, USA. tnnguyen61@uh.edu.
² Department of Chemistry, University of Houston, 3585 Cullen Boulevard, Fleming Building Room 112, Houston, TX 77204-5003, USA. pchen25@central.uh.edu.
³ Department of Chemistry, Faculty of Science, Silpakorn University, Nakhon Pathom 73000, Thailand. krit_set@silpakorn.edu.
⁴ Department of Chemistry, University of Houston, 3585 Cullen Boulevard, Fleming Building Room 112, Houston, TX 77204-5003, USA. jmay@uh.edu.

PMID: 30208621
PMCID: PMC6225256
DOI: 10.3390/molecules23092317

Abstract

Organocatalysis has emerged as a powerful synthetic tool in organic chemistry in the last few decades. Among various classes of organocatalysis, chiral diol-based scaffolds, such as BINOLs, VANOLs, and tartaric acid derivatives, have been widely used to induce enantioselectivity due to the ability of the hydroxyls to coordinate with the Lewis acidic sites of reagents or substrates and create a chiral environment for the transformation. In this review, we will discuss the applications of these diol-based catalysts in different types of reactions, including the scopes of reactions and the modes of catalyst activation. In general, the axially chiral aryl diol BINOL and VANOL derivatives serve as the most competent catalyst for most examples, but examples of exclusive success using other scaffolds, herein, suggests that they should not be overlooked. Lastly, the examples, to date, are mainly from tartrate and biaryl diol catalysts, suggesting that innovation may be available from new diol scaffolds.

Keywords: BINOL; TADDOL; allylation; asymmetric catalysis; conjugate addition; diol catalyst; organoboronates; organocatalysts.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

**Scheme 1**
Common chiral diol-based organocatalysts.

**Scheme 2**
Asymmetric allylboration of ketones and proposed transition state.

**Scheme 3**
Asymmetric crotylboration of acetophenone.

**Scheme 4**
Asymmetric allylation of acyl imines.

**Scheme 5**
Asymmetric crotylboration of benzoyl imines and proposed transition state.

**Scheme 6**
Asymmetric Petasis allylation.

**Scheme 7**
Asymmetric Petasis crotylation.

**Scheme 8**
Reductive allylation of enals.

**Scheme 9**
Diastereoselective reductive crotylations.

**Scheme 10**
Asymmetric methallylation of ketones.

**Scheme 11**
Allylboration of ketones with geranylboronic acid.

**Scheme 12**
Asymmetric propargylation of ketones.

**Scheme 13**
Diastereoselective propargylation of ketones.

**Scheme 14**
Asymmetric arylboration of acyl imines.

**Scheme 15**
Asymmetric vinylboration of acyl imines.

**Scheme 16**
Asymmetric alkynylboration of acyl imines.

**Scheme 17**
Proposed transition state for asymmetric boronate addition.

**Scheme 18**
Enantioselective addition of boronates to vinyl o-QMs.

**Scheme 19**
Enantioselective addition of boronates to hydroxybenzyl ethyl ethers.

**Scheme 20**
Multicomponent boronate condensation reactions.

**Scheme 22**
Proposed mechanism for chroman formation.

**Scheme 23**
Allene synthesis via alkynyl boronates.

**Scheme 24**
Allene synthesis from alkynyl aldehydes.

**Scheme 25**
Conjugate addition of alkynyl boronic esters.

**Scheme 26**
Conjugate addition of alkenyl boronic esters.

**Scheme 27**
Conjugate addition of alkenyl boronic acids.

**Scheme 28**
Conjugate addition of aryl boronic esters.

**Scheme 29**
Conjugate addition of heteroaryl borate salts.

**Scheme 30**
Enantioselective alkenylboronate addition to N-acyl quinoliniums.

**Scheme 31**
Proposed catalytic cycle for EEDQ addition.

**Scheme 32**
Enantioselective oxidative C–H alkenylation and arylation.

**Scheme 33**
Asymmetric conjugate addition catalyzed by tartaric acid derivatives.

**Scheme 35**
Asymmetric Petasis reaction catalyzed by VAPOL.

**Scheme 36**
Asymmetric aziridination reaction with VAPOL iminium boroxinate.

**Scheme 37**
Enantioselective protonation of silyl enol ethers.

**Scheme 38**
Enantioselective acyl Mannich reaction with silanediol catalysis.

**Scheme 39**
Alkylation reactions of various chromenones.

**Scheme 40**
Hydrocyanation catalyzed by TADDOL.

**Scheme 41**
TADDOL-catalyzed enantioselective Diels–Alder reaction.

**Scheme 42**
TADDOL-catalyzed vinylogous Mukaiyama aldol reaction.

**Scheme 43**
Asymmetric nitroso aldol reaction.

**Scheme 44**
Enantioselective Mukaiyama aldol reaction.

**Scheme 45**
Asymmetric Mukaiyama aldol reaction of ketoesters.

**Scheme 46**
Asymmetric Hetero-Diels–Alder reaction Catalyzed by BAMOL.

**Scheme 47**
Asymmetric hetero-Diels–Alder reaction catalyzed by chiral ferrocenyl diols.

**Scheme 48**
Structures of hydroxyarylalcohols (HAROLs).

**Scheme 49**
Asymmetric Morita–Baylis–Hillman reaction catalyzed by HAROLs.

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Chiral Diol-Based Organocatalysts in Enantioselective Reactions

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Chiral Diol-Based Organocatalysts in Enantioselective Reactions

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