It-R ,-TH - &) - 1b: Organic Chemistry Cumulative Exam

ORGANIC CHEMISTRY CUMULATIVE EXAM
September 7, 2007
"Selective Ring Expansion Alkylation of Formyl[2.2.1]bicyclic Carbinols with
C-Nucleophiles: A Unique Route to Cyclopentane Derivatives," Yang, T.-F.;
Tseng, C.-H.; Wu, K.-I.; Chang, C.-N. J. Org. Chern. 2007 72, 7034-7037.
1.(06) The core bicyclo[2.2.1] structure in use here is important in the
development of mechanistic chemistry, especially carbocation chemistry,
involving a multi-decade dispute among chemists. What is the name of the
specific structure referred to this way?
Either norbornyl cation" or "non-classical carbocation".
2.(10) Structure 2 is said to react by an "anionic oxy-Cope" reaction. What
reagents ar involved, and that would the product(s) be?
(5) that can deprotonat the -OR and (5), (-2 for enol)
3.(10) Treatment of 1 with tosyl acid (Ref. 2) yields the following product.
Give valid curved-arrow mechanisms for itsd production.
4.(16) In the reactions of 8 and 9: What is the structure and chemical purpose
of "TMO"? Of "TEMPO"?
(4+4) Me3N+-O-; OXidizing souce (actually the stoichiometric one)
(4+4) 2,2,6,6-tetramethylpiperidine-N-oxide radical; catalyst.
I want actual structures here, not Just restatement of given names
5.(32) a.(6) Give a valid step-wise curved-arrow mechanism for the conversion
of 7 to the product diol. Yes, Fig. 2 does it in an all-in-one-step method,
but there are aspects to this question that require step-wise nalysis.
--> -
OJ::t- 09' 0)'1-( l( <;'6"
(LJ
b.(6) Experimentally, how would you verify your mechanism, in regard to the
IWo oxygens' locations? What would you do and observe?
70 labeling of (probably) carbonyl 0 via the hydrate. Nmr shows label in the
C3-0 of product. Note: D labeling of OH for ehe KIE is no good; that washes
out in solvents, and its transfer is not the rate-determining step anyway.
c.(6) Now consider an alternate to Fig 2: migration of the tertiary bridgehead
carbon, rather than the quaternary carbon. What product(s) would this produce,
and are they the same or different from that in Fig 2?
Different by where the R group ends up, *and* by which oxygen is which.
d.(8) Discuss the pros and cons of the two possible migrating groups in this
specific case in c.
Note: discussing steric hindrance to R attack has no part in this; that does
not affect migration of one versus the other alkyl, in the preceding step,
In both 6 and 7, the more substituted alkyl group migrates consistently.
Stepwise, this could be written as a carbanion shift to the nominally cationic
(in a resonance form) carbon of the carbonyl; the more substituted alkyl
should be *worse*, being less stable and harder to form as an intermediate.
However, it's likely this is just a concerted l,2-alkyl shift, so a free C
isn't involved. Change in ring strain is also a possible factor.
e.(6) Discuss the rearrangement step in terms of orbital symmetry (think about
the carbonyl group in terms of one of its resonance forms). Allowed or not,
and why?
*If concerted(l) , this is a 2 electron sigmatropic supra-supra case, allowed
(as are carbocations shifts).
6.(16) Structures 6 and 7 both yield alkylated cis-diols upon treatment with
carbanions, but the diols in the products from 6 are endo, and are exo in
those from 7.
a. Why the difference? Illustrate your answer with a curved-arrow mechanism
for 6 to 11, as was done in part Sa, above, but also say why.
The core reason is that the starting functionalities in 6 and 7 are epimeric.
That sets the final geometry, as long as (1) in both cases the more
substituted carbon migrates, and (2) the nucleophilic Grignard attacks from
t ~ ~ ~ : m ~ j t e l ~ ~ = M
0<.-\ ~ CJ 6" (J{
b. Give a reason why the attack of the second carbanion in 6 to 11 is on the
face shown, which is the opposite to that from 7.
The oxyanion and associated counterion keep the nucleophile from that face in
both molecules. This appears more important than the gem-dimethyls on the
bridge blocking that face in 6. The gem-dimethyls in 7 affect either face
equally, so they don't matter in this explanation.
7.(10) In the experimental section:
a. (5) In the last lines of "dihydroxylation of 8", starting with "Anal.
Calcd.", what specific technique is being referred to here? Why the difference
between "Calcd" and "Found"?
Combustion elemental analysis. Calcd is based on expected molecular formula
and isotopic natural abundance; Found is the combustion result.
b. (5) In the last lines of "Preparation of 7". what does HRMS mean?
High Resolution Mass Spectrometry"

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