ORGANIC CHEMISTRY STANDARD TUTORIAL SHEET 2nd YEAR

Organoboron and organosilicon chemistry

Reading Lecture course: Heteroatoms in Organic Synthesis, Prof. D. M. Hodgson

S. E. Thomas, Organic Synthesis – the Roles of Boron and Silicon, Primer #1
J. Robertson, Protecting Group Chemistry, Primer #95 (Chapter 4)

Topics for notes

Boron
Structure and Lewis acidity of trivalent B; 6–8–6 valence electron reactivity patterns
Preparation via alkene and alkyne hydroboration; key reagents
Reactions: protonation, oxidation, amination, addition of carbon nucleophiles, carbonylation
Stereoselective alkene synthesis
Allyl boranes and boron enolates

Silicon
Length and polarisation of C–Si bond; strength of Si–O and Si–F bond; O→O and C→O migrations
SN at and α- to Si
Use in alkoxide-trapping and protecting group chemistry; Si-centred reagents
Olefination reactions
Preparation and reactions of silyl enol ethers
Stabilisation of α-negative and β-positive charge
Reactivity of vinyl, aryl, and allyl/propargyl/allenyl silanes

Tutorial Problems
Provide mechanisms and full explanations for the following, identifying structures for products
where not shown, and commenting on aspects of regio- and stereoselectivity where relevant. The
final section – Further questions – will be covered during the tutorial if time permits.

Boron

(1) BH3·THF then the reagent shown. (2)

AcOD Me Me Me H
1) B2H6
NH2Cl OH
Me Me Me
NaOH, H2O2 2) 160 °C
3) NaOH, H2O2
N2 CN I2, NaOMe

Br CO2Et , t-BuOK

(3)
OSO2Me
Me BH3·THF then Me
Me
Me Me NaOH, H2O2 Me
ORGANOBORON AND ORGANOSILICON CHEMISTRY 2nd YEAR
(4)
1) Cy2BH H Me
Bu Me
2) I2, NaOH Bu Cy

(5)
1) Cy2BH
Bu Br Cy
Bu
2) NaOMe
3) MeCO2H

(6)
Me Me 1) Me NaCN then (CF3CO)2O O
BH2 ?
then NaOH, H2O2 Et Me
Me Me 2) Et

(7)
O
ClBH2·SMe2 then Cl2CHOMe, t-BuOLi
?
Me then NaOH, H2O2

OH

Me

(8)
Me Me
1) Me Me
BH2 H
Me Me
H
MeO 2) CO, H2O then MeO
NaOH, H2O2 then
HCl

(9)
OH
i-PrCHO then
Me B i-Pr
OH
H2N Me

Me
OH
i-PrCHO then
B i-Pr
OH
H2N Me

Silicon

(1)
O O
OSiMe2t-Bu OSiMe2t-Bu
+ Me Li
Me

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ORGANOBORON AND ORGANOSILICON CHEMISTRY 2nd YEAR
(2)
Ph Et2NH Ph
OH OSiMe3
Ph Ph
SiMe3 H

(3)
Et MCPBA then Et Et
H+, H2O
SiMe2Ph OSiMe2Ph
Me BF3·OEt2 Me Me CHO
(Z)- (Z)-

(4) Identify the diol diastereomer giving rise to E- or Z-oct-4-ene under the conditions shown.
OH H+, H2O
Pr KH Pr Pr
Pr Pr Pr
or BF3·OEt2
OH

(5)
SiMe3
O 1) CHO
MeO Li
Me Me
Me 2) H+, H2O Me

(6)
1)
Me3Si MgCl
O (2 equiv.)
CO2Et
Cl CO2Et
2) t-BuOK SiMe3

(7)
O 1) Me3SiCl, Et3N O 1) xs. LDA, Me3SiCl Me O
heat –78 °C Me
Me Me Me
Me Me
2) t-BuCl, SnCl4 2) t-BuCl, SnCl4
Me Me

(8)
O O
1) Me3SiCl, Et3N, ZnCl2
Me Me
2) MVK, heat
O
'MVK' 3) H+, H2O

(9)
Me

OSiMe3 NO2 , SnCl4 then H2O NaOEt

or C9H14O2 O
Me EtOH
N2
O , Cu(acac)2 then H2O

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ORGANOBORON AND ORGANOSILICON CHEMISTRY 2nd YEAR
(10)
Me 1) Li, EtOH, liq. NH3 Me
OMe then Me3SiCl OMe

O 2) t-BuCl, TiCl4 O
H
Me Me
Me
(11)
Me CO2H
SiMe3
HNO3, Ac2O Br2
? ?
SiMe3

(12)
SiMe3 DCl D BUT
Ph Ph
SiMe3 Br2 Me
Et Et
DCl
Ph Ph Me SiMe3
SiMe3 D

(13)
O O
Cl SnCl4
+ SiMe3

(14)
Me Me O Me O
SnCl4
+
Me3Si Me Me Cl Me
Me Me

(15)
OAc
Me3Si
OR TiCl4 OR
O O

(16)
O
1) NaBH4
N N
SiMe3
2) CF3CO2H
O O

(17) How could the overall transformation be achieved in less steps? [Hint: organosulfur chemistry]
O 1) LDA
1) TsNHNH2
O 2) BuLi (2 equiv.) then Me3SiCl
Me
Me then Me3SiCl Me 2) Zn, CH2I2 Me O
Me 3) MeCOCl, AlCl3 Me 3) H+, H2O Me

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ORGANOBORON AND ORGANOSILICON CHEMISTRY 2nd YEAR
Further questions

(B1)
O
O H
BH3·THF then
Me
Me NaOH, H2O2
Me
Me CHO

(B2)
R
R R
1) I2, KHCO3 BH3·THF then
H
O H
2) DBU Bu4N+F–
CO2H CO2H
O

(B3)
Me Me
BH2
Me Me Bu H
Bu I C C
then NaOMe, MeOH H Bu
99% (E)-

(B4) How would you effect the following conversions using organoboron reagents at some stage in
the synthesis. [more than one step will be required in each case]

O Me
(a) OH Br (c)
Me
Me
O
O H
(b) (d)
Me Me OH
Me

(Si1)
OH 1) Me2Si(Cl)CH2Br, Et3N OH

Me Ph 2) Bu3SnH, AIBN, heat Me Ph

3) KF, H2O2
OH

(Si2)
O then t-BuMe2SiO
+
Me SiMe2t-Bu Me Li Me i-Pr
Br Me
i-Pr

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ORGANOBORON AND ORGANOSILICON CHEMISTRY 2nd YEAR
(Si3)
O O
Me Me
Me Me
SnCl4
+ SiMe3
Me C SiMe3 Me
H

(Si4)
O Me OH OH
1) Me3SiCN, cat. CN– 1) AgF, H2O Me

2) MeLi 2) BF3·OEt2
O Me3SiO CN OH

(Si5)
OEt
HO
TsOH, heat TiCl4
+ HO SiMe3 C12H22OSi

(Si6)
OSiMe3 OH
OMe
TiCl4
+
Me3Si OMe
H OMe

(Si7)
O
1) heat
Me3Si + O C8H8O3
2) PhSO3H
O (can be resolved)

(Si8)
Me3Si HO
1) CF3CO3H CO2Me
H
2) BF3·OEt2 H
CO2Me

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