ic961454t_si_001.pdf (1.32 MB)
Ferrocenoyl Amino Acids: A Synthetic and Structural Study†
journal contribution
posted on 1997-05-21, 00:00 authored by Heinz-Bernhard Kraatz, Janusz Lusztyk, Gary D. EnrightA series of ester-protected amino acids were coupled to
ferrocenecarboxylic acid (1) using the DCC/HOBt
protocol
to give ferrocenoyl N-amino acids (amino acid =
Glu(OBz)2 (2a), Gly(OEt)
(2b), Pro(OBz) (2c),
Cys(SBz)OMe
(2d), Ala(OBz) (2e), Tyr(OBz)
(2f), Phe(OBz) (2g)). All products were
fully characterized. The intermediate
hydroxybenzotriazole active ester FcCOOBt (3) was isolated
and fully characterized. The solid state structures
of 2a, 2d, and 3 were determined by
single-crystal X-ray diffraction. 2a: monoclinic
P21 with a =
11.8142(5)
Å, b = 9.7560(5) Å, c =
22.9456(10) Å, β = 90.246(5)°, V =
2644.7(2) Å3, Z = 2, R =
0.046. 2d: orthorhombic
P212121 with
a = 9.957(2) Å, b = 11.680(2) Å,
c = 36.452(2) Å, V = 4239.5(13)
Å3, Z = 4, R = 0.065.
The
solid state structures of 2a and 2d show
extensive CO···H−N hydrogen bonding. 3:
triclinic P1̄ with a =
7.0391(5) Å, b = 10.7922(7) Å, c
= 11.1690(7) Å, α = 108.071(5)°, β =
107.957(5)°, γ = 103.896(5)°, V
=
712.5(2) Å3, Z = 2, R =
0.030. The long ester bond distance of 1.427(2) Å provides a
rationale for its inherent
reactivity toward primary and secondary amines.