Construction of β to carbonyl stereogenic centres by asymmetric 1,4-addition of alkylzirconocenes to dienones and ynenones

Article abstract of DOI:10.1039/c8cc01201f

Copper-catalyzed asymmetric 1,4-addition of alkylzirconium species to linear α,β,γ,δ unsaturated dienones and ynenones is reported. A variety of alkyl nucleophiles are introduced with good yields and excellent regio- and enantio-selectivities to give tertiary carbon centres bearing multiple functional groups. The method is also applicable to an ynethioate with ee's over 96%.

Full text of DOI:10.1039/c8cc01201f

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ISSN 1359-7345
COMMUNICATION
Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc3N@C2n (2n 68 and 80). Synthesis of the
first methanofullerene derivatives of Sc N@D5h-C80
=
3
rsc.li/chemcomm

tꢉꢋꢈꢂꢋ 'ꢄ ꢇꢄꢎ ꢈ'ꢃꢅꢂꢎ ꢐꢈꢆ(ꢁꢇꢂ
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DOI: 10.1039/C8CC01201F
Wꢀꢁꢂꢃꢄꢅ bꢄꢆꢇ
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ꢉꢖꢗꢘꢄꢙꢙꢑꢐꢑꢀꢃ ꢀꢒ ꢄꢅꢚꢕꢅ ꢑꢂꢍꢀꢃꢀꢍꢇꢃꢇꢌ ꢐꢀ ꢙꢑꢇꢃꢀꢃꢇꢌ ꢄꢃꢙ ꢕꢃꢇꢃꢀꢃꢇꢌ
wꢋꢍꢋꢁ)ꢋ' ꢒꢒꢎꢀ Wꢈꢇꢅꢈꢆꢌ ꢑꢒꢓꢓ!
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!ꢍꢍꢋ+ꢎꢋ' ꢒꢒꢎꢀ Wꢈꢇꢅꢈꢆꢌ ꢑꢒꢓꢓ
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ꢂꢇ!ꢀꢂꢐꢇꢙꢋ ! &ꢄꢂꢑꢇꢐꢕ ꢀꢒ ꢄꢅꢚꢕꢅ ꢃꢁꢍꢅꢇꢀ!'ꢑꢅꢇꢌ ꢄꢂꢇ ꢑꢃꢐꢂꢀꢙꢁꢍꢇꢙ ꢊꢑꢐ' ꢎꢀꢀꢙ
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ꢄꢅꢌꢀ ꢄ!!ꢅꢑꢍꢄꢔꢅꢇ ꢐꢀ ꢄꢃ ꢕꢃꢇꢐ'ꢑꢀꢄꢐꢇ ꢊꢑꢐ' ꢇꢇ*ꢌ ꢀ&ꢇꢂ +,-ꢋ
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EtS
O
R1
O
R3
R1
17 example
over 99% ee
R1
n
R2
24 examples
up to 95% ee
up to 96% ee
!ꢂꢌꢐꢐꢋꢎꢆꢁꢍ ꢍꢄꢇꢃꢅ(ꢈꢎꢋ ꢈ''ꢁꢎꢁꢄꢇ 5!/!6 ꢁꢂ ꢈ +ꢄ7ꢋꢆꢏꢅꢉ ꢐꢋꢎꢀꢄ'
"
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O
R1
R2
O
ꢐꢋꢎꢀꢄ'ꢂ ꢅꢂꢋ' ꢎꢄ ꢈ'' ꢈꢉ8ꢌꢉ (ꢆꢄꢅ+ꢂ! ꢇꢄꢇ$ꢂꢎꢈ1ꢁꢉꢁ9ꢋ'
ꢄꢆ(ꢈꢇꢄꢐꢋꢎꢈꢉꢉꢁꢍ ꢆꢋꢈ(ꢋꢇꢎꢂ ꢈꢆꢋ ꢅꢂꢋ' ꢈꢂ ꢇꢅꢍꢉꢋꢄ+ꢀꢁꢉꢋꢂ! 7ꢀꢁꢍꢀ ꢉꢁꢐꢁꢎꢂ
ꢄꢇ ꢎꢀꢋ ꢂꢄ+ꢀꢁꢂꢎꢁꢍꢈꢎꢁꢄꢇ ꢄꢏ ꢎꢀꢋ ꢈꢉ8ꢌꢉ ꢅꢇꢁꢎ ꢈꢇ' ꢏꢅꢇꢍꢎꢁꢄꢇꢈꢉ (ꢆꢄꢅ+ꢂ
O
Previous
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This
work
R3
R1
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up to 97% ee
ꢑ
20 examples
up to 93% ee
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O
R1
O
ꢂ+ꢋꢍꢁꢋꢂ! (ꢋꢇꢋꢆꢈꢎꢋ' ꢁꢇ ꢂꢁꢎꢅ ꢏꢆꢄꢐ ꢈꢉ8ꢋꢇꢋꢂ ꢈꢇ' /+ꢑùꢆI/ꢉ! 7ꢀꢁꢍꢀ
ꢈꢉꢉꢄ7 ꢀꢁ(ꢀꢉꢌ ꢋꢇꢈꢇꢎꢁꢄꢂꢋꢉꢋꢍꢎꢁ)ꢋ ꢍꢄꢇꢂꢎꢆꢅꢍꢎꢁꢄꢇ ꢄꢏ β$ꢍꢀꢁꢆꢈꢉ ꢍꢋꢇꢎꢆꢋꢂ
SEt
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ꢈꢉ8ꢋꢇꢌꢉ (ꢆꢄꢅ+ꢂ ꢈꢎꢎꢈꢍꢀꢋ' ꢎꢄ ꢎꢀꢋ ꢇꢋ7ꢉꢌ ꢏꢄꢆꢐꢋ' ꢂꢎꢋꢆꢋꢄꢍꢋꢇꢎꢆꢋ 51ꢉꢅꢋ
ꢐꢄꢉꢋꢍꢅꢉꢋꢂ ꢁꢇ {ꢍꢀꢋꢐꢋ "6
O
R1
R2
n
up to 97% ee
R2
21 examples
up to 95% ee
R1
11 examples
up to 91% ee
Çꢄ ꢄ1ꢎꢈꢁꢇ ꢎꢀꢋꢂꢋ ꢅꢇꢂꢈꢎꢅꢆꢈꢎꢋ' ꢎꢈꢆ(ꢋꢎꢂ 5ꢂꢀꢄ7ꢇ ꢁꢇ 1ꢉꢅꢋ ꢁꢇ
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/ꢅ$ꢍꢈꢎꢈꢉꢌ9ꢋ' ꢐꢋꢎꢀꢄ'ꢂ ꢎꢄ ꢍꢄꢇꢂꢎꢆꢅꢍꢎ
D ꢍꢀꢁꢆꢈꢉ ꢍꢋꢇꢎꢆꢋꢂ ꢏꢆꢄꢐ
'ꢁꢋꢇꢄꢇꢋꢂ ꢈꢇ' ꢎꢀꢋ Cꢋꢆꢁꢇ(ꢈ"; ꢈꢇ' Iꢄ)ꢋꢌ'ꢈ"< (ꢆꢄꢅ+ꢂ ꢆꢋ+ꢄꢆꢎꢋ'
ꢈꢂꢌꢐꢐꢋꢎꢆꢁꢍ "$? ꢈ''ꢁꢎꢁꢄꢇꢂ ꢎꢄ 'ꢁꢋꢇꢄꢈꢎꢋꢂ Cꢁꢉꢉꢁꢄꢇ ꢋꢎ ꢈꢉ "? ꢋꢓꢈꢐꢁꢇꢋ'
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{ꢍ$ꢍꢈꢎꢈꢉꢌ9ꢋ' ꢈꢂꢌꢐꢐꢋꢎꢆꢁꢍ "$? ꢈ''ꢁꢎꢁꢄꢇꢂ ꢄꢏ ꢄꢓꢁꢇ'ꢄꢉꢋꢂ ꢎꢄ ꢉꢁꢇꢋꢈꢆ
'ꢁꢋꢇꢌꢉ 8ꢋꢎꢄꢇꢋꢂ
Çꢀꢁꢂ ꢃꢄꢅꢆꢇꢈꢉ ꢁꢂ ꢊ Çꢀꢋ wꢄꢌꢈꢉ {ꢄꢍꢁꢋꢎꢌ ꢄꢏ /ꢀꢋꢐꢁꢂꢎꢆꢌ ꢑꢒꢓꢓ
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tꢉꢋꢈꢂꢋ 'ꢄ ꢇꢄꢎ ꢈ'ꢃꢅꢂꢎ ꢐꢈꢆ(ꢁꢇꢂ

tꢉꢋꢈꢂꢋ 'ꢄ ꢇꢄꢎ ꢈ'ꢃꢅꢂꢎ ꢐꢈꢆ(ꢁꢇꢂ
ChemComm
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DOI: 10.1039/C8CC01201F
/haaÜbL/!ÇLhb
Wꢀꢁꢂꢃꢄꢅ bꢄꢆꢇ
Çꢈ1ꢉꢋ ꢑ wꢋꢈꢍꢎꢁꢄꢇ ꢍꢄꢇ'ꢁꢎꢁꢄꢇꢂ ꢈꢇ' ꢂꢍꢄ+ꢋ ꢄꢏ ꢈꢉ8ꢋꢇꢋꢂ
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[Cp2ZrHCl] DCM;
CuCl (10 mol%), AgOTf (11 mol%)
Ligand A (10 mol%)
R1
[Cp2ZrHCl] DCM;
CuCl (10 mol%), AgOTf (11 mol%)
Ligand A (10 mol%)
1
+
O
R1
O
Ph
O
O
O
O
+
P N
nBu
R1
Ph
R1
Ph
nBu
TMSCl (5.0 eq)
Ph
TMSCl (5.0 eq)
2a
3
A
Et2O, ice bath, overnight
Et2O, ice bath, overnight
1i
2
3
Entry
Substrate
Product
Cy
Yield [%]a
ee [%]b
Yield [%]a ee [%]b
Entry
1
Substrate
O
Product
Ph
O
2b
3i
3j
61
65
97
96
O
1a
1b
3a
1
2
70
70
90
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Ph
O
2c
2d
2
3
3b
92
O
O
O
O
3k
3l
87
-
92
-
Ph
O
O
Ph
O
2e
2f
4
3
4
5
1c
1d
1e
3c
3d
3e
78
79
78
63
92
86
O
Br
Br
Br
O
O
O
O
O
TBDMSO
Me3Si
O
5c
3m
3n
53
70
47
43
TBDMSO
Cl
Cl
O
6c
2g
2h
Si
O
O
O
Br
O
7c
3o
63
86
Br
6
1f
3f
78
92
O2N
O2N
O
O
O
Cl
O
8d
2i
2j
3p
3q
51
77
54
95
Ph
Ph
1g
1h
3g
3h
7
85
60
90
90
Cl
O
Br
9d,e
SEt
8c
SEt
Br
O
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{ꢅ++ꢄꢆꢎꢁꢇ( ꢁꢇꢏꢄꢆꢐꢈꢎꢁꢄꢇ6O ꢋꢇꢈꢇꢎꢁꢄꢐꢋꢆꢁꢍ ꢋꢓꢍꢋꢂꢂ 7ꢈꢂ 'ꢋꢎꢋꢆꢐꢁꢇꢋ' 1ꢌ It[/ ꢄꢆ
{C/ 2ꢔ 7ꢈꢂ ꢅꢂꢋ' ꢁꢇꢂꢎꢋꢈ' ꢄꢏ 2ꢄ
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ꢋꢓꢍꢋꢂꢂ 7ꢈꢂ 'ꢋꢎꢋꢆꢐꢁꢇꢋ' 1ꢌ It[/ ꢄꢆ {C/ ꢉꢒ 7ꢈꢂ ꢅꢂꢋ' ꢁꢇꢂꢎꢋꢈ' ꢄꢏ ꢉꢑꢋ 9ꢎꢀꢌꢉꢋꢇꢋ
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5/a ꢈꢇ' 9ꢎꢑh 5"-"6
Lꢇ ꢍꢄꢇꢎꢆꢈꢂꢎ ꢎꢀꢋ ꢂꢋꢉꢋꢍꢎꢁ)ꢋ "!;$ꢈ''ꢁꢎꢁꢄꢇ +ꢆꢄ'ꢅꢍꢎꢂ ꢄꢏ ꢇꢄꢇ$
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ꢎꢄ ꢐꢄꢂꢎ !/!ꢂ 7ꢁꢎꢀ ꢈꢉ8ꢌꢉ9ꢁꢍꢄꢇꢄꢍꢋꢇꢋꢂ ꢎꢀꢋ ꢍꢈꢎꢈꢉꢌꢂꢎ ꢉꢄꢈ'ꢁꢇ( ꢍꢈꢇ 1ꢋ
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ꢑ#
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7ꢀꢋꢇ 7ꢋ 'ꢋꢍꢆꢋꢈꢂꢋ' ꢎꢀꢋ ꢈꢐꢄꢅꢇꢎ ꢄꢏ {ꢍꢀ7ꢈꢆꢎ9 ꢆꢋꢈ(ꢋꢇꢎ ꢎꢄ " < ꢋK
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ꢂꢎꢅ'ꢁꢋꢂ ꢄꢇ ꢆꢋꢉꢈꢎꢋ' ꢂꢌꢂꢎꢋꢐꢂ ꢈꢆꢋ ꢅꢇ'ꢋꢆ7ꢈꢌ wꢋꢐꢈꢆ8ꢈ1ꢉꢌ! ꢅꢇ'ꢋꢆ
ꢎꢀꢋꢂꢋ ꢍꢄꢇ'ꢁꢎꢁꢄꢇꢂ ꢇꢄ "!?$ꢈ''ꢅꢍꢎ 7ꢈꢂ ꢄ1ꢂꢋꢆ)ꢋ' ꢈꢎ ꢈꢉꢉ Çꢀꢋ ꢂꢍꢄ+ꢋ
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íꢋ ꢏꢄꢅꢇ' ꢎꢀꢈꢎ !/! ꢄꢏ ꢈꢉ8ꢌꢉ9ꢁꢆꢍꢄꢇꢁꢅꢐ ꢂ+ꢋꢍꢁꢋꢂ ꢎꢄ ꢉꢁꢇꢋꢈꢆ
=!>!C!D$ꢅꢇꢂꢈꢎꢅꢆꢈꢎꢋ' 'ꢁꢋꢇꢄꢇꢋꢂ! ꢌꢇꢋꢇꢄꢇꢋꢂ! ꢈꢇ' ꢌꢇꢋꢎꢀꢁꢄꢈꢎꢋꢂ ꢏꢄꢆꢐꢂ
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1ꢋꢈꢆ
ꢈ ꢏꢅꢇꢍꢎꢁꢄꢇꢈꢉ (ꢆꢄꢅ+ Çꢀꢋ ꢆꢋꢈꢂꢄꢇ ꢏꢄꢆ ꢎꢀꢋ ꢋꢓꢍꢋꢉꢉꢋꢇꢎ
ꢆꢋ(ꢁꢄꢂꢋꢉꢋꢍꢎꢁ)ꢁꢎꢌ ꢄ1ꢂꢋꢆ)ꢋ' ꢀꢋꢆꢋ ꢁꢂ ꢍꢅꢆꢆꢋꢇꢎꢉꢌ ꢅꢇꢍꢉꢋꢈꢆ Lꢇ ꢍꢄꢇꢎꢆꢈꢂꢎ
2 % Wꢀ bꢁꢂꢃ ! ꢑꢒ"ꢑ! ꢈꢈ! "$#
Çꢀꢁꢂ ꢃꢄꢅꢆꢇꢈꢉ ꢁꢂ ꢊ Çꢀꢋ wꢄꢌꢈꢉ {ꢄꢍꢁꢋꢎꢌ ꢄꢏ /ꢀꢋꢐꢁꢂꢎꢆꢌ ꢑꢒꢓꢓ
tꢉꢋꢈꢂꢋ 'ꢄ ꢇꢄꢎ ꢈ'ꢃꢅꢂꢎ ꢐꢈꢆ(ꢁꢇꢂ

tꢉꢋꢈꢂꢋ 'ꢄ ꢇꢄꢎ ꢈ'ꢃꢅꢂꢎ ꢐꢈꢆ(ꢁꢇꢂ
ChemComm
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DOI: 10.1039/C8CC01201F
Wꢀꢁꢂꢃꢄꢅ bꢄꢆꢇ
/haaÜbL/!ÇLhb
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ꢅꢇꢂꢈꢎꢅꢆꢈꢎꢋ' /$/ 1ꢄꢇ'ꢂ 5ꢋꢇꢎꢆꢁꢋꢂ ꢑ! #6! ꢈ +ꢆꢄꢎꢋꢍꢎꢋ' ꢈꢉꢍꢄꢀꢄꢉ 5ꢋꢇꢎꢆꢌ "6 ëꢁꢇꢌꢉꢍꢌꢍꢉꢄꢀꢋꢓꢈꢇꢋ ꢉꢄ 7ꢈꢂ ꢁꢇꢎꢆꢄ'ꢅꢍꢋ' 7ꢁꢎꢀ 1ꢄꢎꢀ (ꢄꢄ'
5ꢋꢇꢎꢆꢌ ;6! ꢈ ꢂꢁꢉꢈꢇꢋ 5ꢋꢇꢎꢆꢌ <6! ꢀꢈꢉꢄ(ꢋꢇꢂ 5ꢋꢇꢎꢆꢁꢋꢂ ?! @6 ꢈꢉꢉ 7ꢄꢆ8ꢋ' ꢌꢁꢋꢉ' ꢈꢇ' ꢋꢋ 5A@H! .<H ꢋꢋ! ꢋꢇꢎꢆꢌ ꢑ6 ꢈꢇ' ꢈꢉ8ꢋꢇꢋꢂ 1ꢋꢈꢆꢁꢇ(
7ꢋꢉꢉ 7ꢁꢎꢀ ꢎꢀꢋ ꢋꢓꢍꢋ+ꢎꢁꢄꢇ ꢄꢏ 'ꢁꢋꢇꢋ ꢉꢍ íꢋ ꢏꢄꢅꢇ' ꢈ ꢂꢎꢌꢆꢋꢇꢋ ꢅꢇꢂꢈꢎꢅꢆꢈꢎꢋ' /$/ 1ꢄꢇ'ꢂ 5ꢋꢇꢎꢆꢁꢋꢂ #! ;6! +ꢆꢄꢎꢋꢍꢎꢋ' ꢈꢉꢍꢄꢀꢄꢉꢂ 5ꢋꢇꢎꢆꢌ
'ꢋꢆꢁ)ꢈꢎꢁ)ꢋꢂ ꢍꢄꢅꢉ' 1ꢋ ꢈ''ꢋ' ꢁꢇ ?ꢒH ꢌꢁꢋꢉ' ꢈꢇ' .ꢒH ꢋꢋ! ꢈꢉꢎꢀꢄꢅ(ꢀ
Çꢈ1ꢉꢋ ; !''ꢁꢎꢁꢄꢇꢂ ꢎꢄ ꢌꢇꢋꢇꢄꢇꢋꢂ ꢈꢇ' ꢌꢇꢋꢎꢀꢁꢄꢈꢎꢋꢂ
ꢀꢋꢆꢋ ꢂꢄꢐꢋ "!?$ꢈ''ꢅꢍꢎ 7ꢈꢂ ꢄ1ꢂꢋꢆ)ꢋ' 5"!; ꢎꢄ "!? ꢆꢈꢎꢁꢄ Qꢑꢒ-"6
[Cp2ZrHCl] DCM;
5ꢋꢇꢎꢆꢌ A6! ꢀꢄ7ꢋ)ꢋꢆ ꢁꢇ ꢎꢀꢁꢂ ꢍꢈꢂꢋ 2ꢔ 7ꢈꢂ ꢎꢀꢋ ꢂꢎꢈꢆꢎꢁꢇ( 'ꢁꢋꢇꢄꢇꢋ ꢈꢇ'
CuCl (10 mol%), AgOTf (11 mol%)
R1
O
O
Ligand A (10 mol%)
ꢁꢎ ꢐꢁ(ꢀꢎ 1ꢋ ꢎꢀꢈꢎ ꢈ ꢎꢋꢆꢐꢁꢇꢈꢉ ꢈꢆꢄꢐꢈꢎꢁꢍ ꢆꢁꢇ( ꢄꢇ ꢎꢀꢋ +ꢄꢉꢌꢋꢇꢋ
+ꢆꢄꢐꢄꢎꢋꢂ ꢂꢋꢉꢋꢍꢎꢁ)ꢁꢎꢌ ꢁꢇ ꢏꢈ)ꢄꢅꢆ ꢄꢏ ꢍꢄꢐ+ꢉꢋꢎꢋ "!;$ꢈ''ꢁꢎꢁꢄꢇ
+
R1
R2
R2
TMSCl (5.0 eq)
Et2O, ice bath, overnight
Ph
Ph
Çꢄ ꢏꢅꢆꢎꢀꢋꢆ ꢁꢇ)ꢋꢂꢎꢁ(ꢈꢎꢋ! 7ꢋ ꢋꢓꢈꢐꢁꢇꢋ 'ꢁꢏꢏꢋꢆꢋꢇꢎ 'ꢁꢋꢇꢄꢇꢋꢂ
ꢅꢂꢁꢇ( ꢄꢅꢆ +ꢆꢋ)ꢁꢄꢅꢂ ꢍꢄꢇ'ꢁꢎꢁꢄꢇꢂ ꢈꢇ' ꢈꢉ8ꢋꢇꢋ ꢉꢑ 5Çꢈ1ꢉꢋ ꢑ6 !ꢉ8ꢌꢉ
ꢂꢅ1ꢂꢎꢁꢎꢅꢎꢋ' 'ꢁꢋꢇꢄꢇꢋꢂ 2ꢔ ꢈꢇ' 2ꢍ 5ꢋꢇꢎꢆꢁꢋꢂ "! ꢑ6 1ꢄꢎꢀ ꢈꢏꢏꢄꢆ'ꢋ'
"!;$+ꢆꢄ'ꢅꢍꢎꢂ 7ꢁꢎꢀ ꢄ)ꢋꢆ ?ꢒ H ꢌꢁꢋꢉ' ꢈꢇ' .?H ꢋꢋ ꢈꢉꢎꢀꢄꢅ(ꢀ ꢈ ꢂꢐꢈꢉꢉ
ꢈꢐꢄꢅꢇꢎ ꢄꢏ "!? ꢈ''ꢅꢍꢎꢂ 7ꢋꢆꢋ ꢈꢉꢂꢄ ꢄ1ꢂꢋꢆ)ꢋ' 5"!; ꢎꢄ "!? ꢆꢈꢎꢁꢄ
Qꢑꢒ-"6 íꢀꢋꢇ ꢎꢀꢋ 1ꢅꢉ8ꢁꢋꢆ 'ꢁꢐꢋꢎꢀꢌꢉ ꢂꢅ1ꢂꢎꢁꢎꢅꢎꢋ' 'ꢁꢋꢇꢄꢇꢋ 2ꢙ 7ꢈꢂ
ꢎꢋꢂꢎꢋ'! ꢇꢄ "!? ꢈ''ꢅꢍꢎ 7ꢈꢂ ꢄ1ꢎꢈꢁꢇꢋ' 5ꢋꢇꢎꢆꢌ #6 íꢁꢎꢀ 'ꢁꢋꢇꢄꢈꢎꢋ
2ꢇ ꢇꢄ ꢆꢋꢈꢍꢎꢁꢄꢇ 7ꢈꢂ ꢄ1ꢂꢋꢆ)ꢋ' ꢄ)ꢋꢆꢇꢁ(ꢀꢎ ꢈꢇ' 2ꢇ 7ꢈꢂ ꢆꢋꢍꢄ)ꢋꢆꢋ'
{ꢋ)ꢋꢆꢈꢉ 'ꢁꢋꢇꢄꢇꢋꢂ 7ꢁꢎꢀ 'ꢁꢏꢏꢋꢆꢋꢇꢎ ꢂꢅ1ꢂꢎꢁꢎꢅꢎꢋꢂ ꢄꢇ ꢎꢀꢋ ꢈꢆꢄꢐꢈꢎꢁꢍ
ꢆꢁꢇ(ꢂ 5ꢋꢇꢎꢆꢁꢋꢂ <$@6 7ꢋꢆꢋ ꢋꢓꢈꢐꢁꢇꢋ' 7ꢁꢎꢀ ꢈ ꢉꢄꢂꢂ ꢄꢏ ꢋꢇꢈꢇꢎꢁꢄꢍꢄꢇꢎꢆꢄꢉ
ꢂꢋꢋꢇ 7ꢁꢎꢀ ꢋꢉꢋꢍꢎꢆꢄꢇ 'ꢄꢇꢈꢎꢁꢇ( ꢈꢆꢄꢐꢈꢎꢁꢍꢂ ꢈꢇ' (ꢄꢄ' ꢆꢋꢂꢅꢉꢎꢂ 7ꢁꢎꢀ
ꢈꢇ ꢋꢉꢋꢍꢎꢆꢄꢇ 7ꢁꢎꢀ'ꢆꢈ7ꢁꢇ( (ꢆꢄꢅ+ ꢎꢄ (ꢁ)ꢋ 3ꢀ ꢁꢇ A?H ꢋꢋ íꢁꢎꢀ
ꢂꢅ1ꢂꢎꢆꢈꢎꢋ 2ꢑꢖ 7ꢀꢋꢆꢋ ꢈ +ꢀꢋꢇꢌꢉ (ꢆꢄꢅ+ ꢆꢋ+ꢉꢈꢍꢋꢂ ꢎꢀꢋ ꢍꢈꢆ1ꢄꢇꢌꢉ
ꢐꢋꢎꢀꢌꢉ (ꢆꢄꢅ+! ꢄꢇꢉꢌ <"H ꢌꢁꢋꢉ' 7ꢁꢎꢀ <;H ꢋꢋ 7ꢈꢂ ꢄ1ꢂꢋꢆ)ꢋ' 5ꢋꢇꢎꢆꢌ
A6 Iꢄ7ꢋ)ꢋꢆ! 'ꢁꢋꢇꢎꢀꢁꢄꢈꢎꢋ 24 (ꢈ)ꢋ )ꢋꢆꢌ (ꢄꢄ' ꢆꢋꢂꢅꢉꢎ 5@@H ꢌꢁꢋꢉ'!
.<H ꢋꢋ! ꢋꢇꢎꢆꢌ .6! ꢈꢇ' ꢎꢀꢋ ꢎꢀꢁꢄꢋꢂꢎꢋꢆ (ꢆꢄꢅ+ ꢍꢄꢅꢉ' 1ꢋ
ꢎꢆꢈꢇꢂꢏꢄꢆꢐꢋ' ꢁꢇꢎꢄ ꢈ ꢆꢈꢇ(ꢋ ꢄꢏ ꢍꢈꢆ1ꢄꢇꢌꢉ 'ꢋꢆꢁ)ꢈꢎꢁ)ꢋꢂ
1
4
5
Yield [%]a
Entry
1
Substrate
Product
O
ee [%]b
1j
5a
70
87
84
69
94
95
96
92
O
1a
1b
1c
1d
5b
2
3
4
5
O
O
5c
5d
5e
TBDMSO
O
66
75
76
94
94
96
TBDMSO
Çꢀꢋ ꢈ1ꢂꢄꢉꢅꢎꢋ ꢍꢄꢇꢏꢁ(ꢅꢆꢈꢎꢁꢄꢇ ꢄꢏ 3! 7ꢈꢂ ꢄ1ꢎꢈꢁꢇꢋ' 1ꢌ
ꢍꢄꢐ+ꢈꢆꢁꢂꢄꢇ ꢄꢏ ꢄ+ꢎꢁꢍꢈꢉ ꢆꢄꢎꢈꢎꢁꢄꢇ 'ꢈꢎꢈ 7ꢁꢎꢀ ꢎꢀꢋ ꢉꢁꢎꢋꢆꢈꢎꢅꢆꢋ".ꢈ
!
ꢂꢁꢐꢁꢉꢈꢆꢉꢌ ꢎꢀꢋ ꢈ1ꢂꢄꢉꢅꢎꢋ ꢍꢄꢇꢏꢁ(ꢅꢆꢈꢎꢁꢄꢇ ꢄꢏ 5ꢄ 5ꢂꢋꢋ 1ꢋꢉꢄ7 ꢈꢇ'
ꢂꢅ++ꢄꢆꢎꢁꢇ( ꢁꢇꢏꢄꢆꢐꢈꢎꢁꢄꢇ6 ꢁꢂ 8ꢇꢄ7ꢇ !ꢉꢉ ꢄꢎꢀꢋꢆ ꢂꢎꢋꢆꢋꢄꢍꢀꢋꢐꢁꢍꢈꢉ
ꢈꢂꢂꢁ(ꢇꢐꢋꢇꢎꢂ ꢁꢇ ꢎꢀꢁꢂ ꢐꢈꢇꢅꢂꢍꢆꢁ+ꢎ ꢈꢆꢋ ꢐꢈ'ꢋ 1ꢌ ꢈꢇꢈꢉꢄ(ꢌ ꢎꢄ 3! ꢈꢇ'
Si
O
1f
5f
6
7
Si
5ꢄ
Br
O
íꢋ ꢈꢉꢂꢄ ꢋꢓ+ꢉꢄꢆꢋ' ꢁꢏ 7ꢋ ꢍꢄꢅꢉ' ꢆꢋ'ꢅꢍꢋ ꢎꢀꢋ ꢈꢐꢄꢅꢇꢎ ꢄꢏ ꢍꢈꢎꢈꢉꢌꢂꢎ
Br
1g
5g
ꢅꢂꢋ' ꢁꢇ ꢎꢀꢋ ꢍꢄꢅ+ꢉꢁꢇ( ꢄꢏ ꢉꢑ ꢈꢇ' 2ꢍ íꢀꢋꢇ ꢎꢀꢋ ꢍꢈꢎꢈꢉꢌꢂꢎ ꢉꢄꢈ'ꢁꢇ(
7ꢈꢂ 'ꢋꢍꢆꢋꢈꢂꢋ' ꢏꢆꢄꢐ "ꢒH ꢎꢄ ꢑ <H! ꢎꢀꢋ ꢌꢁꢋꢉ' ꢈꢇ' ꢋꢋ 7ꢋꢆꢋ ꢇꢄꢎ
ꢈꢏꢏꢋꢍꢎꢋ' ꢈꢎ ꢈꢉꢉ 5ꢎꢈ1ꢉꢋ #Èꢋꢇꢎꢆꢁꢋꢂ "$#6 A;H ꢋꢋ 7ꢈꢂ ꢄ1ꢂꢋꢆ)ꢋ'
Br
O
7ꢀꢋꢇ " ꢑH ꢍꢈꢎꢈꢉꢌꢂꢎ 7ꢈꢂ ꢅꢂꢋ' 1ꢅꢎ ꢋꢋ 'ꢆꢄ++ꢋ' ꢂꢁ(ꢇꢁꢏꢁꢍꢈꢇꢎꢉꢌ 7ꢁꢎꢀ
ꢒ <H ꢍꢈꢎꢈꢉꢌꢂꢎ 5?H ꢋꢋ! ꢋꢇꢎꢆꢌ <6
Br
8c
SEt
1g
1b
5h
5i
66
75
97
96
Çꢈ1ꢉꢋ # /ꢈꢎꢈꢉꢌꢂꢎ ꢉꢄꢈ'ꢁꢇ( ꢂꢎꢅ'ꢌ 7ꢁꢎꢀ 'ꢁꢋꢇꢄꢇꢋ 2ꢍ
O
SEt
9c
[Cp2ZrHCl] DCM;
CuCl (10 mol%), AgOTf (11 mol%)
Ligand A (10 mol%)
Ph
O
O
+
Ph
TMSCl (5.0 eq)
1i
2c
3j
Et2O, ice bath, overnight
wꢋꢈꢍꢎꢁꢄꢇ ꢍꢄꢇ'ꢁꢎꢁꢄꢇꢂ- ꢈꢉ8ꢋꢇꢋ 5ꢑ < ꢋK 6! L/+ꢑùꢆI/ꢉM 5ꢑ ꢋK 6! 5/a 5ꢒ ꢑ ꢐꢉ6!
ꢋꢇꢄꢇꢋ 5" ꢋK 6! ꢍꢄ++ꢋꢆ 5"ꢒ ꢐꢄꢉ H6! ꢉꢁ(ꢈꢇ' 5"ꢒ ꢐꢄꢉ H6! ꢂꢁꢉ)ꢋꢆ 5"" ꢐꢄꢉ H6! Ça{/ꢉ
Entry
Catalyst loading [%]
Yield [%]a
ee [%]b
ꢄ
5< ꢋK 6 ꢁ òꢁꢋꢉ' ꢄꢏ ꢁꢂꢄꢉꢈꢎꢋ' +ꢆꢄ'ꢅꢍꢎ !1ꢂꢄꢉꢅꢎꢋ ꢍꢄꢇꢏꢁ(ꢅꢆꢈꢎꢁꢄꢇ ꢄꢏ 5ꢄ 8ꢇꢄ7ꢇ!
ꢄꢎꢀꢋꢆ ꢈꢂꢂꢁ(ꢇꢐꢋꢇꢎꢂ 1ꢌ ꢈꢇꢈꢉꢄ(ꢌ 5ꢂꢋꢋ {ꢅ++ꢄꢆꢎꢁꢇ( ꢁꢇꢏꢄꢆꢐꢈꢎꢁꢄꢇ6O ꢋꢇꢈꢇꢎꢁꢄꢐꢋꢆꢁꢍ
ꢋꢓꢍꢋꢂꢂ 7ꢈꢂ 'ꢋꢎꢋꢆꢐꢁꢇꢋ' 1ꢌ It[/ ꢄꢆ {C/ ꢑꢒ H ꢍꢈꢎꢈꢉꢌꢂꢎ ꢉꢄꢈ'ꢁꢇ( 7ꢈꢂ ꢅꢂꢋ'
7ꢁꢎꢀ ꢈ ꢐꢁꢓꢎꢅꢆꢋ ꢄꢏ 5/a ꢈꢇ' 9ꢎꢑh 5"-"6 ꢈꢂ ꢂꢄꢉ)ꢋꢇꢎ
1
2
3
4
5
65
63
64
60
63
96
96
96
84
6
10.0
5.0
2.5
1.2
0.5
<6! ꢂꢁꢉꢈꢇꢋꢂ 5ꢋꢇꢎꢆꢌ ?6 ꢈꢇ' ꢀꢈꢉꢄ(ꢋꢇꢂ 5ꢋꢇꢎꢆꢌ @6 ꢍꢄꢅꢉ' ꢈꢉꢉ 1ꢋ
ꢁꢇꢂꢎꢈꢉꢉꢋ' ꢁꢇ ꢈꢆꢄꢅꢇ' @ꢒH ꢌꢁꢋꢉ' 7ꢁꢎꢀ ꢈꢎ ꢉꢋꢈꢂꢎ .ꢑH ꢋꢋ
! ꢌꢇꢋꢎꢀꢁꢄꢈꢎꢋ 7ꢈꢂ +ꢆꢋ+ꢈꢆꢋ' ꢈꢇ' ꢎꢋꢂꢎꢋ' ꢈꢇ'! ꢁꢇ ꢈꢍꢍꢄꢆ'ꢈꢇꢍꢋ
7ꢁꢎꢀ +ꢆꢋ)ꢁꢄꢅꢂ 7ꢄꢆ8! ꢅꢇꢂꢈꢎꢅꢆꢈꢎꢋ' ꢎꢀꢁꢄꢋꢂꢎꢋꢆꢂ ꢈꢆꢋ ꢉꢋꢂꢂ ꢆꢋꢈꢍꢎꢁ)ꢋ
@
ꢎꢀꢈꢇ ꢋꢇꢄꢇꢋꢂ ꢐꢈ8ꢁꢇ( ꢆꢋꢈꢍꢎꢁꢄꢇꢂ ꢂꢉꢄ7ꢋꢆ Lꢇꢍꢆꢋꢈꢂꢁꢇ( ꢎꢀꢋ ꢍꢈꢎꢈꢉꢌꢂꢎ
ꢁ òꢁꢋꢉ' ꢄꢏ ꢁꢂꢄꢉꢈꢎꢋ' +ꢆꢄ'ꢅꢍꢎ ꢄ 9ꢇꢈꢇꢎꢁꢄꢐꢋꢆꢁꢍ ꢋꢓꢍꢋꢂꢂ 7ꢈꢂ 'ꢋꢎꢋꢆꢐꢁꢇꢋ' 1ꢌ It[/
ꢉꢄꢈ'ꢁꢇ( ꢏꢆꢄꢐ "ꢒH ꢎꢄ ꢑꢒH! ꢈꢇ' ꢅꢂꢁꢇ( ꢈ ꢐꢁꢓꢎꢅꢆꢋ ꢄꢏ ꢂꢄꢉ)ꢋꢇꢎꢂ ꢏꢄꢆ
ꢎꢀꢋꢂꢋ ꢈ''ꢁꢎꢁꢄꢇꢂ 5"-" 5/a ꢈꢇ' 9ꢎꢑh6! ꢈꢉꢉꢄ7ꢋ' ꢈꢉ8ꢋꢇꢋꢂ ꢎꢄ 1ꢋ
ꢁꢇꢎꢆꢄ'ꢅꢍꢋ' ꢁꢇ ꢈꢆꢄꢅꢇ' @ꢒH ꢌꢁꢋꢉ' 7ꢁꢎꢀ .?H ꢋꢋ 5ꢋꢇꢎꢆꢁꢋꢂ A! .6
íꢋ ꢇꢋꢓꢎ ꢋꢓꢈꢐꢁꢇꢋ' ꢉꢁꢇꢋꢈꢆ =!>!C!D$ꢅꢇꢂꢈꢎꢅꢆꢈꢎꢋ' ꢂꢅ1ꢂꢎꢆꢈꢎꢋꢂ
ꢏꢋꢈꢎꢅꢆꢁꢇ( ꢎꢆꢁ+ꢉꢋ 1ꢄꢇ'ꢂ! ꢌꢇꢋꢇꢄꢇꢋꢂ ꢈꢇ' ꢌꢇꢋꢎꢀꢁꢄꢈꢎꢋꢂ! ꢎꢄ ꢎꢋꢂꢎ ꢎꢀꢋ
(ꢋꢇꢋꢆꢈꢉꢁꢎꢌ ꢄꢏ ꢄꢅꢆ ꢐꢋꢎꢀꢄ' 5Çꢈ1ꢉꢋ ;6 Üꢂꢁꢇ( ꢈꢉ8ꢋꢇꢋ ꢉ4 ꢈꢇ' ꢎꢀꢋ
Çꢀꢁꢂ ꢃꢄꢅꢆꢇꢈꢉ ꢁꢂ ꢊ Çꢀꢋ wꢄꢌꢈꢉ {ꢄꢍꢁꢋꢎꢌ ꢄꢏ /ꢀꢋꢐꢁꢂꢎꢆꢌ ꢑꢒꢓꢓ
Wꢀ bꢁꢂꢃ ! ꢑꢒ"#! ꢈꢈ! "$# % 3
tꢉꢋꢈꢂꢋ 'ꢄ ꢇꢄꢎ ꢈ'ꢃꢅꢂꢎ ꢐꢈꢆ(ꢁꢇꢂ

tꢉꢋꢈꢂꢋ 'ꢄ ꢇꢄꢎ ꢈ'ꢃꢅꢂꢎ ꢐꢈꢆ(ꢁꢇꢂ
ChemComm
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DOI: 10.1039/C8CC01201F
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[Cp2ZrHCl] DCM;
CuCl (10 mol%), AgOTf (11 mol%)
Ligand A (10 mol%)
O
O
+
TMSCl (5.0 eq)
Ph
Ph
Et2O, ice bath, overnight
1b
Entry
4a
5c
Yield [%]a
ee [%]b
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Catalyst loading [%]
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2
3
4
5
75
80
75
79
71
96
95
95
92
36
10.0
5.0
2.5
1.2
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ChemComm
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DOI: 10.1039/C8CC01201F
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ChemComm
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DOI: 10.1039/C8CC01201F
Construction of β to carbonyl stereogenic centres by asymmetric 1,4-
addition of alkylzirconocenes to dienones and ynenones
Zhenbo Gao and Stephen P. Fletcher*
stephen.fletcher@chem.ox.ac.uk
Department of Chemistry, University of Oxford, Chemistry
Research Laboratory, Mansfield Road, Oxford, OX1 3TA, U.K.
[Cp2ZrHCl] DCM;
CuCl (10 mol%) AgOTf (11 mol%)
R1
R2
O
O
Ligand A (10 mol%)
+
R3
R2
R3
R1
TMSCl (5.0 eq)
16 examples
up to 97% ee
Et2O, ice bath, overnight
[Cp2ZrHCl] DCM;
CuCl (10 mol%) AgOTf (11 mol%)
Ligand A (10 mol%)
TMSCl (5.0 eq)
Et2O, ice bath, overnight
R1
R2
O
O
+
R3
R1
R3
R2
9 examples
up to 97% ee
A new asymmetric addition of alkylzirconium species to dienones, dienthioate,
ynenones, ynethionates with good yields and excellent ee’s is reported.