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Synlett 2007(10): 1490-1500  
DOI: 10.1055/s-2007-980376
ACCOUNT
© Georg Thieme Verlag Stuttgart · New York

Design versus Discovery in Synthetic Applications of Organoalanes

Simon Woodward*
School of Chemistry, The University of Nottingham, Nottingham NG7 2RD, UK
Fax: +44(115)9513564; e-Mail: simon.woodward@nottingham.ac.uk;
Further Information

Publication History

Received 4 January 2006
Publication Date:
06 June 2007 (online)

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Abstract

A discussion focusing on the benefits of considered forethought in proposing new asymmetric catalytic reactions is presented based on the author’s experiences in the areas of copper-promoted 1,4-addition and SN2′ chemistry and in the area of group 10 catalysed coupling reactions of organoaluminium reagents with aldehydes and allylic halides. While high-throughput methods have become the norm for attaining practical procedures in catalytic asymmetric chemistry appropriate strategic planning should not be abandoned in the conception of new catalytic processes.

  • 1 Introduction

  • 2 Design and Discovery in Copper-Based Catalysis

  • 2.1 Serendipity with Thio-Analogues of BINOL

  • 2.2 Design to the Fore in Conjugate Addition

  • 2.3 SN2′ Chemistry: You Can’t Always Get What You Want…

  • 3 Design and Discovery in DABAL-Based Catalysis

  • 3.1 Intelligent Approaches to Asymmetric 1,2-Aldehyde ­Methylation

  • 3.2 Scope of the DABAL-Me3 Reagent

  • 3.3 SN2′ Chemistry: You Can Get What You Want…

  • 4 Summary and Outlook

Key words

enones - aldehydes - asymmetric - catalysis - organo­metallics

    References and Notes

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12

Calculations were carried out using Spartan (www.wavefun.com) for Mac ‘02 to generate equilibrium geometries at using the semi-empirical PM3; Chapron, A. unpublished results.

13

The CSD database was accessed via: www.ccdc.cam.ac.uk.

18

The transition states G/H are conjectures; they could not be attained by PM3 calculation.

19

The enolates were prepared by the chemistry of ref. 15. Neat Ac2O (2.5 equiv) was added and the temperature raised from -45 to +6 °C over 6 h. ( Z )-(3 S )-1,3-Dimethyloct-1-enyl Acetate 1H NMR (400.1 MHz, CDCl3): δ = 0.87 (3 H, t, J = 7.2 Hz, CH2 Me), 0.91 (3 H, d, J = 6.7 Hz, CHMe), 1.19-1.39 [8 H, m, -(CH2)4-], 1.87 (3 H, d, J = 0.9 Hz, =CMe), 2.17 (3 H, s, COMe), 2.34 (1 H, m, CHMe), 4.77 (1 H, dd, J = 9.8, 0.9 Hz, =CH). Irradiation of the olefinic =CH signal (δ = 4.77 ppm) produced a 3.6% NOE at the enol methyl (δ = 1.87 ppm) consistent with a Z double-bond geometry. 13C NMR (100.6 MHz, CDCl3): δ = 15.5 (Me), 19.5 (Me), 21.1 (Me), 22.7 (CH2), 27.0 (CH2), 30.6 (CH), 32.0 (CH2), 37.2 (CH2), 123.4 (=CH), 143.8 (=COAc), 169.1 (C=O). IR (CHCl3): νmax = 1741 (C=O) cm-1. HRMS (EI): m/z calcd for C12H22O2 [M]: 198.1620; found [M+]: 198.1620.
( E )-(3 S )-1,3-Dimethyloct-1-enyl Acetate
1H NMR (400.1 MHz, CDCl3): δ = 0.88 (3 H, t, J = 7.2 Hz, CH2 Me), 0.98 (3 H, d, J = 6.7 Hz, CHMe), 1.19-1.39 [8 H, m, -(CH2)4-], 1.84 (3 H, d, J = 0.9, =CMe), 2.09 (3 H, s, COMe), 2.34 (1 H, m, CHMe), 4.88 (1 H, dd, J = 10.1, 0.9 Hz, =CH). Irradiation of the olefinic =CH signal (δ = 4.88 ppm) produced only a 1.7% NOE at the C(3) methyl (δ = 0.91 ppm) consistent with an E double-bond geometry. 13C NMR (100.6 MHz, CDCl3): δ = 14.1 (Me), 20.7 (Me), 21.3 (Me), 22.7 (CH2), 27.1 (CH2), 31.9 (CH), 32.0 (CH2), 37.7 (CH2), 123.9 (=CH), 144.4 (=COAc), 169.6 (C=O). IR (CHCl3): νmax = 1741 (C=O) cm-1. HRMS (EI): m/z calcd for C12H22O2 [M]: 198.1620; found [M+]: 198.1602.

37

I am indebted to Prof. D. Gillheany (UCD, Ireland) for this advice; he assures me it arose in the K. B. Sharpless group in the 1990s. It’s not always true, but is commonly observed.

47

My sincere thanks to both Charles Davis (of Sigma-Aldrich) and John Blacker (at NPILPharma) for their advice and insights into the world of commercial chemistry. DABAL is now available from Sigma-Aldrich (catalogue no. 68210-1 DABAL-trimethylaluminium).

51

El Hajjaji, S.; Woodward, S. unpublished results.

55

Novak, A.; Woodward, S. unpublished results.