X-ray structural investigations of bromo-oxoditerpenoids and the nickel (II) chelate of a pyridoxal-amino acid intermediate

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X-RAY STRUCTURAL IM/ESTTGATIffi

nGIP]}:[AI-'.AI.{U{O ACID ^.mEB}€DTATE

':i

.&

fhesis

Pres,ented

to The University of Auctlaftfl

for thF

Degrc-q,of,

Doctor

o-f, P,trillosophy

by

John Frarrklin Clntfield

Jutren 1WA.

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This thesis is presented in tvro pa:.ts"

PART

A is concerned with the crystal structure o.f nickcl(fI) pyridoxylidene L-valinc.

PART

B

embodies

the structural str.rdies of three

5-bromo-J-oxoditerpenoids and the subsequent detcr;nination

of the stereochernistry of

tr,ro

of these

compounds.

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FAET

A

.-!i-

AqFFact

The cry'stal structure

of,

E{g-(pyrfdorylidme-L- vaLine)niet,el(r:) hydrate (refenred, to as nictef(ff)

p:midslsylidene L-valine) has

beqa dlilteard,iled

but the

dlif;ficr*Ity in dletectLng enal,l deyiatlong

.f,rorn

body-ceotred

s

nql€tflrr

and.

in Locatl,ng aLl

^gotrrfeOt

arolequlee,

lrae

prreciluded

an accuate alrallysisi

O_ctahedral

coo+&[oation ts

the ni€kel aton lg achievEd by t&e attacl!rust o'f tvo 8.ehtff,

base units. The

f,ueed.

ltug

sy4gte4

of

^each

ulrlt reveds

d,istortions from planarity.

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Chapter

-

1

2

3

4PP'endices

A

B

c

D

2 3

4 Diag,ranxs

PABT

4

-_CoryfSI-Ts

fntreduatJon

The.Struetunal, fnvestigatlote

of,

[l*eX( I'r) Pyrfdorqg,lldere t-Valine Discussiotr alld

Conflmeions

Elreetion

Cogiines

(for the

ingoing:

and dltffl'acted

beauS)

Standard Deviations E'J.l{psolds clf Vibratlon

Tables of

Orrs-ercred

$tnueture A,nplitudes

aud

Oalclrlatedl Structure Fdctors

Bond Lerlgths

Bond AngX.es'

The

lfol.ecular

Packing

Fage

1

11 64

6,0

6t

62 63

&2 71 73 v5

v7

R,ef,erences 78

-

X_Uustr-ati._ons

Figtrre 1 A lrbleetile Viewea

dqwn

the

c-axLs