New Functionalized Grignard Reagents and their Applications in ...

34 downloads 125 Views 1MB Size Report
"Practical Synthetic Procedures: Preparation and Reactions of .... 7.1 Synthesis of ortho-Nitro-Functionalized Aryl and Heteroaryl Grignard Reagents 96.
!

!

"##$

-

% +

',,.

&'( )* + ( * / ! * +

*

!

0 '2+ -

0

!

6 6

*

"##$

! ! !

",+

* 1

3

'+ 5 "+ 5

+$

+ +

'2+ -

"##$

+ / ! +1 * 7 "'+ - "##$

% 4

+

8

! +

9! * 4

/ ! 0

3

+

40

+

!

0

+

7

+

+

+

7 + +1 4

+

7

*

7:; 0 + + 8+ ! 4 *7 !! 4

!

+

)!

!

7 * 0 ? 5 / 0 3 * 4 / * / 440 8 * / 0 0 / 440 @ / A 09 * * + %4 ! 8 :@ 7 C ) C +

0 )

5 7 7 0 + = + %4

44 +

*

+ C

B

*0 0 B+ 8 !

/7 7 B! * 0 @ * 0 ! *

7

4

73 44 0

0

7!

0 5+ /

0 3+ B ! 0 1+ %!

4+

74 ! 7 4

7 +

+1 * 0 +

+=

!

)

44

! /

4

44

3 + =+ %

"##$

/ !

*

+

-

! +

+

+

"##'

7 !

!

0

44 8

*

0

7

!

+ 7

7 7 7 + +D8

7

! E

+

+

! '+F )+ G ! ! )7

"#" %7

$ %

0 =+ ! @

%

&

0 3+ % 4 ! 6 4 G 0 '(('0

0

+

$+F 3+ % 4 *7 )

0 +/ ! 3 '(('0

G5

4 !

! G

? 7 0 'I.# 'I.' J

'(('0

+ / !

4

G

I+F 3+ % 4 * *

G) ? ! ? '((*0 ,22 ,2.+

4

9

0 +/ ! G 0 + / ! )7 0 ,'2 ,'.J

.+F 3+ % 4 0 1+ B 4 7 *7 ? 4 + ,+F

+ 4 0 +B 7 )7 7/ G ",I. ",K#+

* 0

7 ?

@

G? @

5

%

G%7 ?

0 +/ ! G

0 ?+ 5 ! '(()0

!

!

7 G

) G

) 7 !

*7 '(()0

'0( '0(

'0$ '0$

)

7

G

)7 0 .,K ,##+ ? !@

0 3+ % 4 0 8+ -+ / 0 5+ ) 7 7 ) ! '((*0 0 (#". (#(#J

!

! ?

) ! '((*0

+ / ! 4

0 =+ 0 + ) 7) 7

''+F + / ! 0 = + C+ )+ C G1 7 ! G $(#" $("#+

7 4

0

'#+F 3+ % 4 "

+ / ! !

0 'I'# 'I''+

2+F + / 440 3+ % 4 ) ! ..2+

K+F 3+ % 4 7 ! '((*0

C 0

70 C+ B 0 )+ B 0 + / 440 %+ ! 0 3+ % 4 0 %+ = ! 0 8+ ! ! 7 G

0 + / ! 0 G) ? 5 ! )7 '(('0 0 ,(,# ,(,'+

)

70 C+ ) @ !

+

"+F + / ! 0 + 1 4 0 = + 0 + + 70 ?+ % 0 3+ 0 C+ C ) 0 H+ B G ! 4 + (+F 3+ % 4 1

+

8 7

% * G

7

0 +/ ! 4

4 '((*0

7 4

G

! !! 0

G) ? 3 7 ! '((*0

!

0

)7

+

0 + +/ 0 + / 440 8+ / 9 ! 4 "0 $$(. $$2IJ

0 3+ % 4 1 '(()0

0

+ ,

-

$"

+

""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""" . '+ 9

+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ (

'+'

4

9

'+" )

@ !

"+ 9*>! (+

4

++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ,

++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ '2

4

! !

(+' 3 (+"

!

?

3

?

! 4

$+

$+"

7 !

7

2+ %7

+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ((

7

!

7

4

874 I#

) ++++++++++++++++++++++++ $$

*7

)

!

+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ $K

!

7

)7 !

*7 ?

?

7 !

1

+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ $$

4

2+' 3

874 "# !

!

!

7

4

4

!

1

?

)7

)7

2+"

7

#

3

4 $+' 3

3

!

++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ 'K

!

!

1

+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ 'I !

I' !

7

+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ 'I

4

(+(

++++++++++++++++++++++++++++++++++++++++++++++++++++++++ $

*7

4

)

)7

++++++++++++++++ I2

+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ I2 !

++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ II

I+ 5

7

)

7++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ." I+' 3

!

)7

5 4

K+ %

!

7

9

K+( %7

)44 !

B

7

++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ .(

B

7

+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ .$

+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ,I

K+' %7 K+" %7

8

+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ."

I+" I+(

!

? ! 7

!

)7

! !?

! ?

1

75

) 75 )

@ @

!5

,I +++++++++++ ,.

@

+++ ,,

K+$ %7 )

7 !5

) 7 7

@

K+2 5

7

%

+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ '##

1

/

)7

7

!

B

7

+++++++++++++++++++++++++++++++++++++++++++++++++++ '#"

""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""""".()

.+ 5

++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++'#2

,+ 874 ! 4 !

L8 F ++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++'#.

,+' 874 ! 4 !

L8 'F+++++++++++++++++++++++++++++++++++++++++++++ '#.

,+" 874 ! 4 !

L8 "FI' ++++++++ '#.

,+( 874 ! 4 !

4

!

!

!

!

L8 (F+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ '#.

,+$ 874 ! 4 ! *7?

!

4 4

*

! 4

7

,+2 874 ! 4 !

4

!

4 7

!

7

L8 $F ++++++++++++++++++++++++++++++++++++ '#.

!

!

*4

!

!

L8 2F+++++++++++++++++++++++++++++++++++++++++++++++++++++ '#,

,+I 874 ! 4 ! *7?

!

4 4

*

! 4

7

,+K 874 ! 4 ! 7

4 7

!

!

*4

7

L8 IF ++++++++++++++++++++++++ '#,

!

!

L8 KF+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ''#

,+. 874 ! 4 !

4 4

7

,+, 874 ! 4 !

4 4

7

L8 .F +++++++++++++++++++++ ''# 7

L8 ,F

+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ''# ,+'# 874 ! 4 ! 7

!

!

L8 '#F+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ '''

,+'' 874 ! 4 !

L8 ''F++++++++++++++++++++++++++++++++++++++++++++++++++ '''

,+'" 874 ! 4 !

!

*

=

@

L8 '"F+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ''' ,+'( 874 ! 4 ! !

7

,+'$ 874 ! 4 ! !

4

!

4

,+'2 874 ! 4 !

4 7

!

L8 '(F+++++++++++++++++++++++++++++++++++++++++++++++++++ ''' 7

7

L8 '$F +++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ''" 44

!

7

L8

'2F++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ''"

'#+

4

!

3

?

!

''+

4

7

!

7

!

)7

'(+ 5

!

*7

4

?

7

*7

@ 7

) '$+ @

!

)7

'"+ %7

1

!

++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ''(

7

!

7

++++++++++++++++++++++ 'K2 )

)7 )7

)

+++++++++++++++++++ "', 8

)44 !

7++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ "$. !

+++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++++ ".'

%% $ )! )!91 44 + B B! * B ! ! 1" " 1 * ! 3

4+ ) %9

M N

3 ? 9 9)! )B 5 5

! 7 ! ! ! 44 7 * 7 * 7! * 7 * * 7 ! ! 7! ! 7 * ! 0 ! * 7 ! ! 4 $% $ 4 47! * $ 7 47 7 7 M ! 4 ! ! 7 7 7 7 7 ! * * ! 4 ! 4 7

% ?B) ? ? @ ?

5

M M M @

+

!! 4

! B 8 ) 8 8 ) 8 4 81 8 8 C

!

* 1

4

! 4 7

!

M

1@ % 4 ! ! 47 4 47 3@ ! 4

!

9

!! 4 * 4 7

4+

4

!

! ! 4 4 4 4 4 M M M

7 ! 7 7

!

@

19 9

" $

7 4 ! ! 47 * 7 ! 7 47 ! 4

!

4

* 4

! 4 * 7 7 7 ! ! ! 7 ! " 74 4 7 $ 7 74 ! 4 !

4 7

+0 1

+, 2

+

"

." 1$ $ 8

! ! ! !!

7 4 ! 4+3 * 7 ! * ! *

!

!

+% ! ! ! * 7 ! 0 !

4 *

! !

! 7 !

!

! 7 !

!

4 *

+ % ! !

4 7 1* 4 * *7 *

4 4

4

!

0 O

!

+ 7

'

!+

44 !

!! 7

4

4 ! 4

7 !

!

*

70 0

! !

!

! ! C! 5 7 7 70

0 4 7

! 4 ! ! 7 ! 4 ! 0 0 ! 0 ! 4 0 M ! ! 7

.&

1

7+" 8

!!

9 !

7 !

74 7 ! ! * 0 ! ! * ! * 7* * ! 7 ! 70 * 7 ! 4 7 + ? 4 !7!

7

! 4

* ! 4 * *7

M + )

!!

!

!

0 ! ! 4

! +

! ! 4 ! 0 ! 7 0 ! 4 0 !!

7

7

4

!

'.$, 7 ! ! *

! '0 ! * ! 4 4

! *

7 +8 ! 7+ +9 * 4 0

* !0 !

!

*

(

!

! *

4 7 ! 4 + 8 7 * !

(

4

! * ! 4

!

+$ * 7

7 4

+

2

.".

!1

.".".

,

B7 ! !

, $

! !

3

7

7 L%! ! G ! +

'F0 !

4 4

!

4 5

4 4 * 5 ! +

7

0 4

!

81 G

4 4

*7

%!

M

!

!" #

.& %7 8 ! !

5

*7

!

! I

7

+ 3 M * P+ ! *

%!

! !

0 0 %!

*

! Q !

!

! !

7

!

*

+

7!

0 * ! L@ PF M * L P"0 4 4 0 7 ! * 4 ! ! * P @ 4* ! 0 7 + 8 * 04 7 4 * !

5 'F

@" ! * + ) +8 *7 * *7 4 ! 4

+ 8 * ! 4 *

!

!

4

7

* ! *7 !

!

7

4 ! 4

!

!

! 4

0! 4

!

7 ! L

7

R

F0

!

4

! 4 4

! 4 ! 4 4 44 4 !

4 !

5

!

!

$

! !0

!

! 7 +8 ! 4 ! 04 ! + 30 0 ! ! 0 @ 4 * 0 * K 4 L%! "F+

$#

&

)

+, ) '($ #

!



%$)

4

!

7 0

!

."."' 0

43

3 ! 0 4 4 8 *7 + S ! 7 4



%$* '(

0

! +'# ) 4

! +

*

* !

* 0

! !

* 4 4

!

!

"

! 7+ ',('

B L%! (F+ % ) ! BQ !

.

7

7

7

7 7 4

*

7 *

' !7!

*

! !

*

!

!

70 + +'"

" !

2

!

! "

!

" ! 2

4

8 L%! 8 *

* 4 ! ! +) 0 4 4 ! ! * '$ $F+ 8 7 0

*

!

M

! *

0. 0

/

!

8

F+

0

!

)&

R

L

I

! 4 +'' 8

1 2

#

@

7 ! 7! 4 ! !

,

!

12

#

5

%

&

'(

-$

+, -$ ) '($#$. $&/ 0 )

!

'&

$#

*

!

+

!

*

0

* !

5 !

0

!

4

*

'(

! * !

!

! !

2

! + *7 C S * 44 ! ! 4 4 7

! 7 5 4

B0

74 6-'2

!

4

'!

$.

,

-$

4

!

L%!

$F+ $

!

$

!

'!

$.

$.

!

$

! 2

"

!

!

3$. 3 ! 3/

*&

3$.4 3 !4 3/4

4

4 7

3 ',,.0 + / ! ! ! * ! *7 *

5

! 0 5 ! !

/

4 4

'!

4 3Q 74 7+ % ! 7 * 7 ! 4

*

6+

0 ! 0

!

!

!

6

!+ ( -$+ 5 -$+ 5

!

4

4 4 ! 4 L%! *

! 'I

2F+ 8 7 4

+ "

"

6

6 + ,

,

-$ '(

! %$

!

!

!

%

! $ /

$# "

5& %7 ) 4 4 L8 F0



%$!

7 !

!

!

0 0 L8 F0 47

7 4

! ! L8!F0

$# "

!5 0 47

L8 F0 47 L8 F 7

I

!

+ !7! 74 8 L8%F0 4 L8 F0 'K L%! IF+

'!

/

6

"

!

!

6

"

6

+ ,

,

-$

!

! % %

!

%

$.

$.

#

!

"#

$.

#"

!

%

%

/



%$! %

%

7

!

6& 3 L%!

! !

!7!

74 8 4 4

7

!7! 4 47 5

!

+

0 ! '. KF+

$# "

'!

/

4 4

$# "

!

+ ,

!

-$ %$

%$

#

'!

#

#

'(

$.

+ ,

#

-$

'( $.

'! "# $

/

7& %7

70 + / !

* ! !

40 ! 7 7

"# $

-$

7

$.

+

! ! 4 44 !

0 4

$.

+ ,

7

8

#

#

/

!

$# "

!

#

#

$.

!

*

44 !

4 *

!

! ! 44 7 0 ! * +""

"#

"'

!0

4 !

!

K

+ 7

!

! ! 0 70 *7

44 ',

7+ ! 7

!

!

3

*7 4 4 !

7+ 8 * +2

! 7 7 7

7

4

+/ ! 0 4 0 ! 7 ! ! 4 0 /+ + ? ! C ! 7! L%! .F+"(

7 ! * !

! 44 ! 0*

*

$. #

#

$. #

# #

#

#

%

%

# %

% #

% #

# # % 895

# # #

: : : :

! !

9 '!

# ;% #

8& 3 ) 4 7 5 4

!

! 7 4 LNF *

0

%

%

7

3/ 3 ! 3 0# ) 3#

C !

0#

7! +

! ) !

4 .(

*7 ! 4 KIT 7 L%!

4

! )+ B+ % *

# %

#
57

! LC ".

!

!

$.

8 (. !?(

# %

# %

# % #

@ .9

'& B 8

!

7 !

*

!

!

7 * *

7

4

+ 4

+

",

,

!

!

+ 8

7

."'".

%

8 L%?) F+ ?

! !

4 ! 4 0 ! * 70 !7

! 40

4 !

! 0

! 4 ! * L VV VB V3F ! # ! !# ! +8 !! ". ''F+

7 4

* 7 .)

4

! 74 ! !

!

*

44

0

! .'T 7

.* %

* L%!

%

%#

% $

%#

%

$%+ !