Configurations of the Monosaccharides Section 1 83.

80

CMO
OH

CHjOH
D-gtycrrmUekj'Je

--
f
CHO

—OH
OH

CH;OH
txnthrose
HO--
1CHO

--
CH,OH
OH

D-thrcosc

1
r
iCHO
--
)

--
CHO CHO CHO
—OH HO -- OH HO--
—OH OH HO --- HO --
— t— OH OH

CH:OH
— —OH
CH.OH
——OH
CH;OH CH2OH
D-nbose D-arabinosc D-xylosc D-lyxose

i
CHO
>H HO
1CHO
—— ---- CHO

—
---- --
OH HO —
--
1CHO

—— --
---- -- --
CHO

--
OH HO--
CHO CHO
OH HO--
--
1CHO

-- -- --
—OH —OH HO HO OH OH HO HO

——
( OH OH OH OH HO HO-- HO HO--
— —
CH:OH
o„ OH

CH2OH
OH
CH.OH
OH
CH.OH
OH
CH.OH
OH

CH2OH
—OH
CH.OH CH.OH
OH

D-allose D-aJtrosc D-glucose D-mannose D-gulose D-idose D-galactose D-talose

FIGURE 18.3. The D-aldoses.

step down in the figure. Therefore, D-glyceraldehyde leads to a pair of tetroses,

each tetrose leads to a pair of pentoses, and each pentose leads to a pair of hexoses.

STUDY PROBLEMS
1 8.4. How many chiral carbon atoms does each of the following aldoses have?
(a) D-talose (b) L-allose (c) D-arabinose

18.5. There are eight D-aldohexoses and also eight L-aldohexoses. Write the Fischer
projections of (a) L-glucose, and (b) L-mannose.

18.6. What is the name of the aldohexose in which only the OH at carbon 5 has the
opposite configuration from that of D-glucose?
814 Chapter 18 Carbohydrates

SECTION 18.4.
Cyclization of the Monosaccharides
Glucose has an aldehyde group at carbon 1 and hydroxyl groups at carbons
4 and 5 (as well as at carbons 2, 3, and 6). A general reaction of alcohols and alde¬
hydes is that of hemiacetal formation (see Section 1 1.8).
O OH
H’
RCH + R'OH RCH— OR'
a hemiacetal

In water solution, glucose can undergo an intramolecular reaction to yield

cyclic hemiacetals. Either five-membered ring hemiacetals (using the hydroxyl
group at carbon 4) or six-membered ring hemiacetals (using the hydroxyl group at
carbon 5) can be formed.
A new chiral carbon is formed
upon cyclization

carbon 4 HO--
CHO
OH
HO
-- OH
OH O
HO

HO
OH O

+
OHJ
OH

CH2OH
D-glucose
OH

CH2OH
-- OH

CH2OH
Fischer projections oj the
hemiacetal fice-membered rings

CHO
OH
OH
OH
HO

-- OH

--
O O
HO HO + HO
carbon 5 OH OH OH

OH

CH2OH CH2OH CH2OH

D-glucose Fischer projections of the
hemiacetal six-membered rings

In the Fischer projections for the cyclic hemiacetals, note that carbon 1 (the
aldehyde carbon), which is not chiral in the open-chain structure, becomes chiral
in the cyclization. Therefore, a pair of diastereomers results from the cyclization.
Because all the hemiacetal structures are in equilibrium with the aldehyde
in water solution, they are also in equilibrium with each other.
5-membered cyclic hemiacetal glucose 6-membered cyclic hemiacetal
(two diastereomers) (open-chain) (two diastereomers)