ISSN 1070-4272, Russian Journal of Applied Chemistry, 2006, Vol. 79, No. 10, pp. 1621!1625. + Pleiades Publishing, Inc., 2006.
Original Russian Text + E.G. Mamedov, 2006, published in Zhurnal Prikladnoi Khimii, 2006, Vol. 79, No. 10, pp. 1642!1646.
AND INDUSTRIAL ORGANIC CHEMISTRY
Asymmetric Diels-Alder Reaction between Acrylates
and Cyclopentadiene in the Presence of Chiral Catalysts
E. G. Mamedov
Institute of Petrochemical Processes, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
Received August 17, 2005; in final from, March 2006
Abstract-Asymmetric Diels-Alder reaction between cyclopentadiene and alkyl and cycloalkyl acrylates in
the presence of new chiral catalysts, BBr
. MentOEt, AlCl
OMent, and BBr(OMent)
, was studied.
Optically active bicyclo[2.2.1]hept-2-ene-5-carboxylates were synthesized. The influence of the reaction con-
ditions on the total and optical yields and on the stereoselectivity of the adducts synthesized was examined.
The asymmetric catalysis is currently under rapid
development. The number of publications on this sub-
ject and the finance assigned to development of this
line tend to increase . Organic reactions per-
formed in the presence of chiral catalysts underlie
modern asymmetric synthesis. A key issue for achieve-
ment of high results in this field is directed synthesis
of new efficient optically active catalysts .
Norbornene and its saturated analogue norbornane
are essential fragments of many important natural
compounds . Today, synthesis of new compounds
containing these moieties attracts the researchers’ at-
tention [63 8]. Synthesis of representatives of this
class of compounds in the optically active form is of
certain theoretical and practical interest.
Among the promising lines of synthesis of opti-
cally active norbornene derivatives is the asymmetric
Diels-Alder reaction (ADAR) in the presence of chiral
catalysts. We described the first example of ADAR
. MentOEt as chiral catalyst in . That
study laid the foundations of an efficient meth-
od of synthesis of optically active derivatives of
norbornene by ADAR, which was further developed
[10, 11] using optically active methyloxy- and bornyl-
Here we report the results of examination of ADAR
between acrylates and cyclopentadiene (CPD) in
the presence of chiral catalysts, aimed at preparation
of optically active norbornene derivatives.
Chiral B- and Al-containing complex catalysts
were synthesized from natural l-(3)menthol; their
characteristics are listed in Table 1.
All chiral catalysts are well soluble in organic sol-
and can be used as homogenous catalysts.
Optically active norbornenecarboxylates XI3XIX
are prepared by ADAR according to the scheme
where R = Et (II, XI), n-Pr (III, XII), i-Pr (IV, XIII),
n-Bu (V, XIV), i-Bu (VI, XV), t-Bu (VII, XVI),
Table 1. Characterization of chiral catalysts
Catalyst ³ Initial compound ³ bp, oC(P, mm Hg) ³ [a]
, deg ³ Reference
. MentOEt ³ MentOEt ³ 1873188 (1) ³ 399.3 ³ 3
OMent ³ l-(3)-MentOH ³ 1813182 (1) ³ 373.5 ³ 
OMent ³ l-(3)-MentOH ³ 1853187 (1) ³ 378.5 ³ 3
³ l-(3)-MentOH ³ 191 (1) ³ 391.7 ³ 3