Difference between revisions of "File:Sherburn's Total Synthesis of (-)-Artigenin.png"

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[1]The first step involves the formation of the boron enolate of the oxazolidinone (right structure), which then is reacted with the given aldehyde(left) to produce this first structure in an approximate 92% yield.
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(I)The first step involves the formation of the boron enolate of the oxazolidinone [1], which then is reacted with the given aldehyde[2] to produce this first structure [3] in an approximate 92% yield.
  
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[2]In the following two steps the chiral alcohol is protected by the creation of an -OTBS group (down left).  After which the oxazolidinone is removes to form a terminal alcohol (far right).
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(II)In the following two steps the chiral alcohol is protected by the creation of an -OTBS group [4].  After which the oxazolidinone is removed to form a terminal alcohol [5].
  
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[3]
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(III)Separately the aldehyde [6], is reduced to an alcohol [7], the alcohol is reacted with thiophosgene (CSCl2) to produce a very reactive C-Cl bond in place of the alcohol[8].
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(IV)The terminal alcohol from structure [5] reacts with the C-Cl bond from structure [8] to produce a combined product [9]
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(V) The conversion from [9] into [10] requires a [[radical carboxyarylation]].
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(VI) The TBDMS protecting groups are then removed [11].
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(VII) The secondary alcohol is selectively removed to yield our target product (-)-Artigenin [12].
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== InChI ==
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[1]InChI=1/C9H10O3/c1-11-8-4-3-7(6-10)5-9(8)12-2/h3-6H,1-2H3
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[2]InChI=1/C14H15NO3/c1-2-6-13(16)15-12(10-18-14(15)17)9-11-7-4-3-5-8-11/h2-8,12H,9-10H2,1H3/b6-2+/t12-/m0/s1
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[3]InChI=1/C23H25NO6/c1-4-18(21(25)16-10-11-19(28-2)20(13-16)29-3)22(26)24-17(14-30-23(24)27)12-15-8-6-5-7-9-15/h4-11,13,17-18,21,25H,1,12,14H2,2-3H3/t17-,18-,21+/m0/s1
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[4]InChI=1/C29H39NO5Si/c1-9-23(27(31)30-22(19-35-28(30)32)17-20-13-11-10-12-14-20)26(36(7,8)29(2,3)4)21-15-16-24(33-5)25(18-21)34-6/h9-16,18,22-23,26H,1,17,19H2,2-8H3/t22-,23-,26+/m0/s1
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[5]InChI=1/C19H32O3Si/c1-9-14(13-20)18(23(7,8)19(2,3)4)15-10-11-16(21-5)17(12-15)22-6/h9-12,14,18,20H,1,13H2,2-8H3/t14-,18+/m1/s1
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[6]InChI=1/C14H22O2Si/c1-14(2,3)17(5,6)13-8-7-11(10-15)9-12(13)16-4/h7-10H,1-6H3
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[7]InChI=1/C13H22O2Si/c1-13(2,3)16(5,6)12-8-7-10(14)9-11(12)15-4/h7-9,14H,1-6H3
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[8]InChI=1/C14H21ClO2SSi/c1-14(2,3)19(5,6)12-8-7-10(17-13(15)18)9-11(12)16-4/h7-9H,1-6H3
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[9]InChI=1/C33H52O5SSi2/c1-15-23(30(41(13,14)33(5,6)7)24-16-18-26(34-8)27(20-24)35-9)22-37-31(39)38-25-17-19-29(28(21-25)36-10)40(11,12)32(2,3)4/h15-21,23,30H,1,22H2,2-14H3/t23-,30+/m1/s1
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[10]InChI=1/C33H52O5Si2/c1-32(2,3)39(10,11)29-17-14-22(19-28(29)37-9)18-24-25(21-38-31(24)34)30(40(12,13)33(4,5)6)23-15-16-26(35-7)27(20-23)36-8/h14-17,19-20,24-25,30H,18,21H2,1-13H3/t24-,25+,30-/m1/s1
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[11]InChI=1/C21H24O7/c1-25-17-7-5-13(10-19(17)27-3)20(23)15-11-28-21(24)14(15)8-12-4-6-16(22)18(9-12)26-2/h4-7,9-10,14-15,20,22-23H,8,11H2,1-3H3/t14-,15+,20-/m1/s1
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[12]InChI=1/C21H24O6/c1-24-18-7-5-13(11-20(18)26-3)8-15-12-27-21(23)16(15)9-14-4-6-17(22)19(10-14)25-2/h4-7,10-11,15-16,22H,8-9,12H2,1-3H3/t15-,16+/m0/s1

Latest revision as of 13:31, 19 May 2010

Sherburn's Total Synthesis of (-)-Arctigenin

The following synthesis begins at the top left and follows the respective arrows to the bottom left product, (-)-Arctigenin.


(I)The first step involves the formation of the boron enolate of the oxazolidinone [1], which then is reacted with the given aldehyde[2] to produce this first structure [3] in an approximate 92% yield.

(II)In the following two steps the chiral alcohol is protected by the creation of an -OTBS group [4]. After which the oxazolidinone is removed to form a terminal alcohol [5].

(III)Separately the aldehyde [6], is reduced to an alcohol [7], the alcohol is reacted with thiophosgene (CSCl2) to produce a very reactive C-Cl bond in place of the alcohol[8].

(IV)The terminal alcohol from structure [5] reacts with the C-Cl bond from structure [8] to produce a combined product [9]

(V) The conversion from [9] into [10] requires a radical carboxyarylation.

(VI) The TBDMS protecting groups are then removed [11].

(VII) The secondary alcohol is selectively removed to yield our target product (-)-Artigenin [12].



InChI

[1]InChI=1/C9H10O3/c1-11-8-4-3-7(6-10)5-9(8)12-2/h3-6H,1-2H3

[2]InChI=1/C14H15NO3/c1-2-6-13(16)15-12(10-18-14(15)17)9-11-7-4-3-5-8-11/h2-8,12H,9-10H2,1H3/b6-2+/t12-/m0/s1

[3]InChI=1/C23H25NO6/c1-4-18(21(25)16-10-11-19(28-2)20(13-16)29-3)22(26)24-17(14-30-23(24)27)12-15-8-6-5-7-9-15/h4-11,13,17-18,21,25H,1,12,14H2,2-3H3/t17-,18-,21+/m0/s1

[4]InChI=1/C29H39NO5Si/c1-9-23(27(31)30-22(19-35-28(30)32)17-20-13-11-10-12-14-20)26(36(7,8)29(2,3)4)21-15-16-24(33-5)25(18-21)34-6/h9-16,18,22-23,26H,1,17,19H2,2-8H3/t22-,23-,26+/m0/s1

[5]InChI=1/C19H32O3Si/c1-9-14(13-20)18(23(7,8)19(2,3)4)15-10-11-16(21-5)17(12-15)22-6/h9-12,14,18,20H,1,13H2,2-8H3/t14-,18+/m1/s1

[6]InChI=1/C14H22O2Si/c1-14(2,3)17(5,6)13-8-7-11(10-15)9-12(13)16-4/h7-10H,1-6H3

[7]InChI=1/C13H22O2Si/c1-13(2,3)16(5,6)12-8-7-10(14)9-11(12)15-4/h7-9,14H,1-6H3

[8]InChI=1/C14H21ClO2SSi/c1-14(2,3)19(5,6)12-8-7-10(17-13(15)18)9-11(12)16-4/h7-9H,1-6H3

[9]InChI=1/C33H52O5SSi2/c1-15-23(30(41(13,14)33(5,6)7)24-16-18-26(34-8)27(20-24)35-9)22-37-31(39)38-25-17-19-29(28(21-25)36-10)40(11,12)32(2,3)4/h15-21,23,30H,1,22H2,2-14H3/t23-,30+/m1/s1

[10]InChI=1/C33H52O5Si2/c1-32(2,3)39(10,11)29-17-14-22(19-28(29)37-9)18-24-25(21-38-31(24)34)30(40(12,13)33(4,5)6)23-15-16-26(35-7)27(20-23)36-8/h14-17,19-20,24-25,30H,18,21H2,1-13H3/t24-,25+,30-/m1/s1

[11]InChI=1/C21H24O7/c1-25-17-7-5-13(10-19(17)27-3)20(23)15-11-28-21(24)14(15)8-12-4-6-16(22)18(9-12)26-2/h4-7,9-10,14-15,20,22-23H,8,11H2,1-3H3/t14-,15+,20-/m1/s1

[12]InChI=1/C21H24O6/c1-24-18-7-5-13(11-20(18)26-3)8-15-12-27-21(23)16(15)9-14-4-6-17(22)19(10-14)25-2/h4-7,10-11,15-16,22H,8-9,12H2,1-3H3/t15-,16+/m0/s1

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